Modified phosphinimine catalysts for olefin polymerization

ABSTRACT

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a continuation-in-part of U.S. Ser. No. 14/447,720,filed on Jul. 31, 2014 which is a continuation-in part of U.S.application Ser. No. 13/200,144, filed on Sep. 19, 2011, which claimspriority to and the benefit of Canadian Application No. 2,742,461, filedJun. 9, 2011.

FIELD OF THE INVENTION

The present invention relates to supported phosphinimine catalysts,which when treated with appropriate amounts of a suitable catalystmodifier, have improved activity and which produce improved polyethylenewith improved reactor operability. Catalyst modifiers comprise at leastone long chain substituted amine and are present in a phosphiniminebased polymerization catalyst prior to its entry into a polymerizationreactor.

BACKGROUND OF THE INVENTION

Gas phase olefin polymerization with single site catalysts has been awell-established art field since the invention of metallocene catalystsover two decades ago. Although single site polymerization catalysts(such as metallocene catalysts, constrained geometry catalysts, andphosphinimine catalysts) are often chosen for their very high activity,the use of such catalysts can lead to reactor fouling especially in afluidized bed gas phase reactor. Such fouling may include polymeragglomeration, sheeting, or chunking, and may ultimately require reactorshut down.

In order to improve reactor operability, several specialized catalystpreparative methods, operating conditions, and additives have been usedto modify the performance of metallocenes and to reduce reactor fouling.

European Pat. Appl. No. 630,910 discusses reversibly reducing theactivity of a metallocene catalyst using a Lewis base compound such asfor example an amine compound.

Long chain substituted alkanolamine compounds in particular, have beenused in combination with metallocenes to reduce the amount of reactorfouling in fluidized bed polymerization processes. The use ofsubstituted alkanolamines in combination with metallocene catalysts toimprove reactor operability and reduce static levels is described inEuropean Pat. Appl. No. 811,638 and in U.S. Pat. Nos. 5,712,352;6,201,076; 6,476,165; 6,180,729; 6,977,283; 6,114,479; 6,140,432;6,124,230; 6,117,955; 5,763,543; and 6,180,736. Alkanolamines have beenadded to a metallocene catalyst prior to addition to a reaction zone, asdescribed in U.S. Pat. Nos. 6,140,432; 6,124,230 and 6,114,479.Alkanolamines have also been added directly to a reactor or otherassociated parts of a fluidized bed reactor processes such as therecycle stream loop as is taught in European Pat. Appl. No. 811,638 andin U.S. Pat. No. 6,180,729 respectively.

There has been no systematic exploration of the effect of long chainsubstituted amines, including monoalkanolamines and dialkanolamines, onsupported phosphinimine catalysts.

SUMMARY OF THE INVENTION

We now report that a supported phosphinimine catalyst which has beentreated with appropriate amounts of a suitable catalyst modifier,operates at higher productivity levels and with reduced associatedreactor fouling. When specific levels of catalyst modifier were added toa supported phosphinimine catalyst, the productivity could be increasedby more than 10%. Surprisingly, treatment of a supported phosphiniminecatalyst with a suitable catalyst modifier, also lead to modified, evenimproved copolymer products, which had increased branching homogeneityand could be used to make cast film having lower gel levels.

The present invention is directed to the use of a catalyst modifiercomprising at least one long-chain amine. Addition of a catalystmodifier to a supported phosphinimine catalyst for use in a gas phasepolymerization reactor, gives very good reactor operability, improvedpolymer product and few reactor discontinuity events. An example of asuitable catalyst modifier is a long chain amine compound such as a C6to C30 hydrocarbyl substituted dialkanolamine.

Provided is a process for polymerizing ethylene and optionally an alphaolefin in a reactor with a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier comprises at leastone long-chain amine compound and is present in an amount to give from1.0 to 4.0 weight percent of catalyst modifier based on the weight ofi), ii) and iii) of the polymerization catalyst.

Provided is a process for polymerizing ethylene and optionally an alphaolefin in a reactor, the process comprising introducing a polymerizationcatalyst into the reactor, the polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.5to 4.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:

R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

Provided is an olefin polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.5to 4.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

Provided is a polymerization process comprising contacting ethylene andat least one alpha olefin with a polymerization catalyst in a gas phasereactor, the polymerization catalyst comprising: i) a phosphiniminecatalyst, ii) an inert support, iii) a cocatalyst, and iv) a catalystmodifier; wherein the catalyst modifier is present in from 0.25 to 6.0weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1; and wherein the polymerizationcatalyst is prepared by adding all of the catalyst modifier to the inertsupport prior to the addition of the phosphinimine catalyst and prior tothe addition of the cocatalyst.

Provided is a polymerization catalyst comprising: i) a phosphiniminecatalyst; ii) an inert support; iii) a cocatalyst; and iv) a catalystmodifier; wherein the catalyst modifier is present from 0.25 to 6.0weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1; and wherein the polymerizationcatalyst is prepared by adding all of the catalyst modifier to the inertsupport prior to the addition of the phosphinimine catalyst and prior tothe addition of the cocatalyst.

In an embodiment of the invention, a catalyst modifier is present infrom 1.0 to 4.0 weight percent based on the weight of i), ii) and iii)of a polymerization catalyst comprising: i) a phosphinimine catalyst;ii) an inert support; iii) a cocatalyst; and iv) a catalyst modifier.

In an embodiment of the invention, a catalyst modifier is present infrom 1.5 to 3.5 weight percent based on the weight of i), ii) and iii)of a polymerization catalyst comprising: i) a phosphinimine catalyst;ii) an inert support; iii) a cocatalyst; and iv) a catalyst modifier.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula:R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl group havinganywhere from 5 to 30 carbon atoms, and n and m are integers from 1-20.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is an hydrocarbyl group having anywhere from 6 to 30 carbon atoms,and n is an integer from 1-20.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹is an hydrocarbyl group having anywhere from 6 to 30 carbon atoms.

In an embodiment of the invention, a phosphinimine catalyst has theformula: (L)(PI)MX₂, where M is Ti, Zr or Hf; PI is a phosphinimineligand having the formula R₃P═N—, where R is independently selected fromthe group consisting of hydrogen, halogen, and C₁-C₂₀ hydrocarbyl; L isa ligand selected from the group consisting of cyclopentadienyl,substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl,and substituted fluorenyl; and X is an activatable ligand.

In an embodiment of the invention, a cocatalyst is selected from thegroup consisting of ionic activators, alkylaluminoxanes and mixturesthereof.

In an embodiment of the invention, the polymerization process is a gasphase polymerization process carried out in a fluidized bed reactor.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows how the productivity of the polymerization catalystimproves when different levels and type of catalyst modifier areincluded in the catalyst formulation. Poly. Run Nos. 7, 9 and 11 forvarious levels of Armostat-1800, relative to baseline Run No. 6. Poly.Run No. 2 for Atmer-163 relative to baseline Run No. 1. Baselinepolymerization runs are where there is no catalyst modifier included inthe catalyst formulation.

FIG. 2 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 1).

FIG. 3 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 1.5 wt % of Atmer-163.

FIG. 4 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 6).

FIG. 5 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 1.5 wt % of Armostat-1800.

FIG. 6 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 2.5 wt % of Armostat-1800.

FIG. 7 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 3.5 wt % of Armostat-1800.

FIG. 8 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 13).

FIG. 9 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence of25 ppm of Atmer-163 added directly to the reactor (based on the weightof the polymer produced).

FIG. 10 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 16).

FIG. 11 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 2.5 wt % of Armostat-1800 (Run No. 17).

FIG. 12 shows the production rate in kg/hour of polymer and the catalystfeeder output (measured as the percentage of the maximum rotation speedof the variable-speed motor of the catalyst feeder, which corresponds tothe rotation speed of the disk in the catalyst feeder) forethylene/1-hexene copolymerization with catalyst A1.

FIG. 13 shows the production rate in kg/hour of polymer and the catalystfeeder output (measured as the percentage of the maximum rotation speedof the variable-speed motor of the catalyst feeder, which corresponds tothe rotation speed of the disk in the catalyst feeder) forethylene/1-hexene copolymerization with catalyst A2.

FIG. 14 shows the production rate in kg/hour of polymer and the catalystfeeder output (measured as the percentage of the maximum rotation speedof the variable-speed motor of the catalyst feeder, which corresponds tothe rotation speed of the disk in the catalyst feeder) forethylene/1-hexene copolymerization with catalyst B1.

FIG. 15 shows the production rate in kg/hour of polymer and the catalystfeeder output (measured as the percentage of the maximum rotation speedof the variable-speed motor of the catalyst feeder, which corresponds tothe rotation speed of the disk in the catalyst feeder) forethylene/1-hexene copolymerization with catalyst B2.

FIG. 16 shows the production rate in kg/hour of polymer and the catalystfeeder output (measured as the percentage of the maximum rotation speedof the variable-speed motor of the catalyst feeder, which corresponds tothe rotation speed of the disk in the catalyst feeder) forethylene/1-hexene copolymerization with catalyst B3.

FIG. 17 shows a gel permeation chromatograph with Fourier transforminfra-red (GPC-FTIR) detection obtained for an ethylene copolymer madeusing catalyst A1. The comonomer content, shown as the number of shortchain branches per 1000 carbons (y-axis), is given relative to thecopolymer molecular weight (x-axis). The upwardly sloping line (fromleft to right) is the short chain branching (in short chain branches per1000 carbons atoms) determined by FTIR. As can be seen in the Figure,the number of short chain branches increases at higher molecularweights, and hence the comonomer incorporation is said to be “reversed”.

FIG. 18a shows a gel permeation chromatograph with Fourier transforminfra-red (GPC-FTIR) detection obtained for an ethylene copolymer madeusing catalyst A2. The comonomer content, shown as the number of shortchain branches per 1000 carbons (y-axis), is given relative to thecopolymer molecular weight (x-axis). The slightly downwardly slopingline (from left to right) is the short chain branching (in short chainbranches per 1000 carbons atoms) determined by FTIR. As can be seen inthe Figure, the number of short chain branches decreases slightly athigher molecular weights, and hence the comonomer incorporation is saidto be “normal”.

FIG. 18b shows a gel permeation chromatograph with Fourier transforminfra-red (GPC-FTIR) detection obtained for an ethylene copolymer madeusing catalyst A3. The comonomer content, shown as the number of shortchain branches per 1000 carbons (y-axis), is given relative to thecopolymer molecular weight (x-axis). The slightly downwardly slopingline (from left to right) is the short chain branching (in short chainbranches per 1000 carbons atoms) determined by FTIR. As can be seen inthe Figure, the number of short chain branches slightly decreases athigher molecular weights, and hence the comonomer incorporation is saidto be “normal”.

FIG. 19 shows a temperature rising elution fractionation (TREF) analysisand profile of an ethylene copolymer made using catalyst B1.

FIG. 20 shows a temperature rising elution fractionation (TREF) analysisand profile of an ethylene copolymer made using catalyst B3.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the present invention, a “catalyst modifier” comprises at least onelong chain amine compound which, when added to a phosphinimine basedpolymerization catalyst in appropriate amounts, can reduce, prevent ormitigate at least one: of fouling, sheeting, temperature excursions, andstatic level of a material in polymerization reactor; and/or can alterthe properties of copolymer product obtained in a polymerizationprocess.

The Catalyst Modifier

In the present invention, carrying out a polymerization reaction with aphosphinimine based polymerization catalyst, which has been treated witha catalyst modifier comprising at least one long chain amine compound,allows for high production rates in a gas phase polymerization reactorwith reduction of at least one of: reactor fouling, reactor staticlevels, catalyst static levels, and reactor temperature excursions.Alterations or improvements to product polymer, and reduction in castfilm gel counts are also obtained.

The catalyst modifier employed in the present invention comprises a longchain amine compound. In the present invention, the terms “long chainsubstituted amine” or “long chain amine” are defined as tri-coordinatenitrogen compounds (i.e. amine based compounds) containing at least onehydrocarbyl group having at least 5 carbon atoms, preferably from 6 to30 carbon atoms. The terms “hydrocarbyl” or “hydrocarbyl group” includesbranched or straight chain hydrocarbyl groups which may be fullysaturated groups (i.e. have no double or triple bonding moieties) orwhich may be partially unsaturated (i.e. they may have one or moredouble or triple bonding moieties). The long chain hydrocarbyl group mayalso contain un-saturation in the form of aromatic ring moietiesattached to or part of the main chain. Preferably, the long chain amine(i.e. the tri-coordinate nitrogen compound) will also have at least oneheteroatom containing hydrocarbyl group. Such heteroatom containinghydrocarbyl groups can be branched or straight chain hydrocarbyl groupsor substituted hydrocarbyl groups having one or more carbon atoms and atleast one heteroatom. Heteroatom containing hydrocarbyl groups may alsocontain unsaturated moieties. Suitable heteroatoms include for example,oxygen, nitrogen, phosphorus or sulfur. Other groups which may beattached to nitrogen in a long chain substituted amine compound aregenerally selected from hydrocarbyl groups having one or more carbonatoms and/or a hydrogen group (H).

In embodiments of the invention, the long chain amine is a long chainsubstituted monoalkanolamine, or a long chain substituteddialkanolamine. These amines have one or two alcoholhydrocarbyl groupsrespectively as well as a hydrocarbyl group having at least 5 carbons.

In an embodiment of the invention, the catalyst modifier employedcomprises at least one long chain amine compound represented by theformula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted monoalkanolamine represented by theformula R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving anywhere from 5 to 30 carbon atoms, R² is a hydrogen or ahydrocarbyl group having anywhere from 1 to 30 carbon atoms, and n is aninteger from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl grouphaving anywhere from 5 to 30 carbon atoms, and n and m are integers from1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and n is an integer from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and n is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a linear hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and n is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH—₂OH)₂ where R¹ is a linear hydrocarbyl group havinganywhere from 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH—₂OH)₂ where R¹ is a linear, saturated alkyl grouphaving anywhere from 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having anywherefrom 8 to 22 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises along chain substituted dialkanolamine represented by the formula:C₁₈H₃₇N(CH₂CH₂H)₂.

In an embodiment of the invention, the catalyst modifier comprises longchain substituted dialkanolamines represented by the formulas:C₁₃H₂₇N(CH₂CH₂OH)₂ and C₁₅H₃₁N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier comprises amixture of long chain substituted dialkanolamines represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having anywherefrom 8 to 18 carbon atoms.

Non limiting examples of catalyst modifiers which can be used in thepresent invention are Kemamine AS990™, Kemamine AS650™, Armostat-1800™,bis-hydroxy-cocoamine, 2,2′-octadecyl-amino-bisethanol, and Atmer-163™.

The long chain substituted amine may also be apolyoxyethylenehydrocarbyl amine.

In an embodiment of the invention, the catalyst modifier comprises apolyoxyethylenehydrocarbyl amine represented by the formula:R¹N((CH₂CH₂O)_(n)H)((CH₂CH₂O)_(m)H), where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbons, and n and m are integers from 1-10 orhigher (i.e. polymeric).

The Polymerization Catalyst

In the present invention, the (olefin) polymerization catalystcomprises: i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier.

The Phosphinimine Catalyst

Some non-limiting examples of phosphinimine catalysts can be found inU.S. Pat. Nos. 6,342,463; 6,235,672; 6,372,864; 6,984,695; 6,063,879;6,777,509 and 6,277,931 all of which are incorporated by referenceherein.

Preferably, the phosphinimine catalyst is based on metals from group 4,which includes titanium, hafnium and zirconium. The most preferredphosphinimine catalysts are group 4 metal complexes in their highestoxidation state.

The phosphinimine catalysts described herein, usually require activationby one or more cocatalytic or activator species in order to providepolymer from olefins.

A phosphinimine catalyst is a compound (typically an organometalliccompound) based on a group 3, 4 or 5 metal and which is characterized ashaving at least one phosphinimine ligand. Any compounds/complexes havinga phosphinimine ligand and which display catalytic activity for ethylene(co)polymerization may be called “phosphinimine catalysts”.

In an embodiment of the invention, a phosphinimine catalyst is definedby the formula: (L)_(n)(PI)_(m)MX_(p) where M is a transition metalselected from Ti, Hf, Zr; PI is a phosphinimine ligand; L is acyclopentadienyl type ligand or a heteroatom ligand; X is an activatableligand; m is 1 or 2; n is 0 or 1; and p is determined by the valency ofthe metal M. Preferably m is 1, n is 1 and p is 2.

In an embodiment of the invention, a phosphinimine catalyst is definedby the formula: (L)(PI)MX₂ where M is a transition metal selected fromTi, Hf, Zr; PI is a phosphinimine ligand; L is a cyclopentadienyl typeligand; and X is an activatable ligand.

The phosphinimine ligand is defined by the formula: R₃P═N—, where Nbonds to the metal, and wherein each R is independently selected fromthe group consisting of a hydrogen atom; a halogen atom; C₁₋₂₀hydrocarbyl radicals which are unsubstituted or further substituted byone or more halogen atom and/or C₁₋₂₀ alkyl radical; C₁₋₈ alkoxyradical; C₆₋₁₀ aryl or aryloxy radical (the aryl or aryloxy radicaloptionally being unsubstituted or further substituted by one or morehalogen atom and/or C₁₋₂₀ alkyl radical); amido radical; silyl radicalof the formula: —SiR′₃ wherein each R′ is independently selected fromthe group consisting of hydrogen, a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀aryl or aryloxy radicals; and germanyl radical of the formula: —GeR′₃wherein R′ is as defined above.

In an embodiment of the invention the phosphinimine ligand is chosen sothat each R is a hydrocarbyl radical. In a particular embodiment of theinvention, the phosphinimine ligand is tri-(tertiarybutyl)phosphinimine(i.e. where each R is a tertiary butyl group, or “t-Bu” for short).

In an embodiment of the invention, the phosphinimine catalyst is a group4 compound/complex which contains one phosphinimine ligand (as describedabove) and one ligand L which is either a cyclopentadienyl-type ligandor a heteroatom ligand.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current invention, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be selected fromthe group consisting of a C₁₋₃₀ hydrocarbyl radical (which hydrocarbylradical may be unsubstituted or further substituted by for example ahalide and/or a hydrocarbyl group; for example a suitable substitutedC₁₋₃₀ hydrocarbyl radical is a pentafluorobenzyl group such as—CH₂C₆F₅); a halogen atom; a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl oraryloxy radical (each of which may be further substituted by for examplea halide and/or a hydrocarbyl group; for example a suitable C₆₋₁₀ arylgroup is a perfluoroaryl group such as —C₆F₅); an amido radical which isunsubstituted or substituted by up to two C₁₋₈ alkyl radicals; aphosphido radical which is unsubstituted or substituted by up to twoC₁₋₈ alkyl radicals; a silyl radical of the formula —Si(R′)₃ whereineach R′ is independently selected from the group consisting of hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

As used herein, the term “heteroatom ligand” refers to a ligand whichcontains at least one heteroatom selected from the group consisting ofboron, nitrogen, oxygen, silicon, phosphorus or sulfur. The heteroatomligand may be sigma or pi-bonded to the metal. Exemplary heteroatomligands include but are not limited to “silicon containing” ligands,“amido” ligands, “alkoxy” ligands, “boron heterocycle” ligands and“phosphole” ligands.

Silicon containing ligands are defined by the formula:—(μ)SiR^(x)R^(y)R^(z) where the “—” denotes a bond to the transitionmetal and μ is sulfur or oxygen. The substituents on the Si atom, namelyR^(x), R^(y) and R^(z) are required in order to satisfy the bondingorbital of the Si atom. The use of any particular substituent R^(x),R^(y) or R^(z) is not especially important. In an embodiment of theinvention, each of R^(x), R^(y) and R^(z) is a C₁₋₂ hydrocarbyl group(i.e. methyl or ethyl) simply because such materials are readilysynthesized from commercially available materials.

The term “amido” is meant to convey its broad, conventional meaning.Thus, these ligands are characterized by (a) a metal-nitrogen bond and(b) the presence of two substituents (which are typically simple alkylor silyl groups) on the nitrogen atom.

The term “alkoxy” is also intended to convey its conventional meaning.Thus, these ligands are characterized by (a) a metal oxygen bond, and(b) the presence of a hydrocarbyl group bonded to the oxygen atom. Thehydrocarbyl group may be a ring structure and may optionally besubstituted (e.g. 2,6 di-tertiary butyl phenoxy).

The “boron heterocyclic” ligands are characterized by the presence of aboron atom in a closed ring ligand. This definition includesheterocyclic ligands which also contain a nitrogen atom in the ring.These ligands are well known to those skilled in the art of olefinpolymerization and are fully described in the literature (see, forexample, U.S. Pat. Nos. 5,637,659 and 5,554,775 and the references citedtherein).

The term “phosphole” is also meant to convey its conventional meaning.“Phospholes” are cyclic dienyl structures having four carbon atoms andone phosphorus atom in the closed ring. The simplest phosphole is C₄PH₄(which is analogous to cyclopentadiene with one carbon in the ring beingreplaced by phosphorus). The phosphole ligands may be substituted with,for example, C₁₋₂₀ hydrocarbyl radicals (which may, optionally, containhalogen substituents); phosphido radicals; amido radicals; silyl oralkoxy radicals. Phosphole ligands are also well known to those skilledin the art of olefin polymerization and are described as such in U.S.Pat. No. 5,434,116.

The term “activatable ligand” refers to a ligand which may be activatedby a cocatalyst (also referred to as an “activator”), to facilitateolefin polymerization. An activatable ligand X may be cleaved from themetal center M via a protonolysis reaction or abstracted from the metalcenter M by suitable acidic or electrophilic catalyst activatorcompounds (also known as “co-catalyst” compounds) respectively, examplesof which are described below. The activatable ligand X may also betransformed into another ligand which is cleaved or abstracted from themetal center M (e.g. a halide may be converted to an alkyl group).Without wishing to be bound by any single theory, protonolysis orabstraction reactions generate an active “cationic” metal center whichcan polymerize olefins. In embodiments of the present invention, theactivatable ligand, X is independently selected from the groupconsisting of a hydrogen atom; a halogen atom; a C₁₋₁₀ hydrocarbylradical; a C₁₋₁₀ alkoxy radical; a C₈₋₁₀ aryl oxide radical, each ofwhich said hydrocarbyl, alkoxy, and aryl oxide radicals may beunsubstituted by or further substituted by a halogen atom, a C₁₋₈ alkylradical, a C₁₋₈ alkoxy radical, a C₈₋₁₀ aryl or aryloxy radical; anamido radical which is unsubstituted or substituted by up to two C₁₋₈alkyl radicals; and a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals. Two activatable X ligandsmay also be joined to one another and form for example, a substituted orunsubstituted diene ligand (i.e. 1,3-diene); or a delocalized heteroatomcontaining group such as an acetate group.

The number of activatable ligands depends upon the valency of the metaland the valency of the activatable ligand. The preferred phosphiniminecatalysts are based on group 4 metals in their highest oxidation state(i.e. 4⁺). Particularly suitable activatable ligands are monoanionicsuch as a halide (e.g. chloride) or a hydrocarbyl (e.g. methyl, benzyl).

In some instances, the metal of the phosphinimine catalyst may not be inthe highest oxidation state. For example, a titanium (III) componentwould contain only one activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula, (L)(PI)MX₂, where M is Ti, Zr or Hf; PI is a phosphinimineligand having the formula R₃P═N—, where R is independently selected fromthe group consisting of hydrogen, halogen, and C₁-C₂₀ hydrocarbyl; L isa ligand selected from the group consisting of cyclopentadienyl,substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl,and substituted fluorenyl; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected from thegroup consisting of cyclopentadienyl, substituted cyclopentadienyl,indenyl, and substituted indenyl; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected from thegroup consisting of a substituted cyclopentadienyl and substitutedindenyl; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a cyclopentadienyl ligand (“Cp” for short) and twochloride or two methyl ligands bonded to the group 4 metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a substituted cyclopentadienyl ligand and twochloride or two methyl ligands bonded to the group 4 metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a perfluoroaryl substituted cyclopentadienylligand and two chloride or two methyl ligands bonded to the group 4metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a perfluorophenyl substituted cyclopentadienylligand (i.e. Cp—C₆F₅) and two chloride or two methyl ligands bonded tothe group 4 metal.

In an embodiment of the invention, the phosphinimine catalyst contains a1,2-substituted cyclopentadienyl ligand and a phosphinimine ligand whichis substituted by three tertiary butyl substituents.

In an embodiment of the invention, the phosphinimine catalyst contains a1,2 substituted cyclopentadienyl ligand (e.g. a 1,2-(R*)(Ar—F)Cp) wherethe substituents are selected from R* a hydrocarbyl group, and Ar—F aperfluorinated aryl group, a 2,6 (i.e. ortho) fluoro substituted phenylgroup, a 2,4,6 (i.e. ortho/para) fluoro substituted phenyl group, or a2,3,5,6 (i.e. ortho/meta) fluoro substituted phenyl group respectively.

In the present invention, 1,2 substituted cyclopentadienyl ligands suchas for example 1,2-(R*)(Ar—F)Cp ligands may contain as impurities 1,3substituted analogues such as for example 1,3-(R*)(Ar—F)Cp ligands.Hence, phosphinimine catalysts having a 1,2 substituted Cp ligand maycontain as an impurity, a phosphinimine catalyst having a 1,3substituted Cp ligand. Alternatively, the current invention contemplatesthe use of 1,3 substituted Cp ligands as well as the use of mixtures ofvarying amounts of 1,2 and 1,3 substituted Cp ligands to givephosphinimine catalysts having 1,3 substituted Cp ligands or mixedphosphinimine catalysts having 1,2 and 1,3 substituted Cp ligands.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbylgroup; Ar—F is a perfluorinated aryl group, a 2,6 (i.e. ortho) fluorosubstituted phenyl group, a 2,4,6 (i.e. ortho/para) fluoro substitutedphenyl group, or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted phenylgroup; M is Ti, Zr or Hf; and X is an activatable ligand. In anembodiment of the invention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is an alkyl group; Ar—F is aperfluorinated aryl group, a 2,6 (i.e. ortho) fluoro substituted phenylgroup, a 2,4,6 (i.e. ortho/para) fluoro substituted phenyl group or a2,3,5,6 (i.e. ortho/meta) fluoro substituted phenyl group; M is Ti, Zror Hf; and X is an activatable ligand. In an embodiment of theinvention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbyl group havingfrom 1 to 20 carbons; Ar—F is a perfluorinated aryl group; M is Ti, Zror Hf; and X is an activatable ligand. In an embodiment of theinvention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a straight chain alkylgroup; Ar—F is a perfluorinated aryl group, a 2,6 (i.e. ortho) fluorosubstituted phenyl group, a 2,4,6 (i.e. ortho/para) fluoro substitutedphenyl group, or a 2,3,5,6 (i.e. ortho/meta) fluoro substituted phenylgroup; M is Ti, Zr or Hf; and X is an activatable ligand. In anembodiment of the invention, the phosphinimine catalyst has the formula:(1,2-(n-R*)(Ar—F)Cp)Ti(N═P(t-Bu)₃)X₂ where R* is a straight chain alkylgroup; Ar—F is a perfluorinated aryl group; M is Ti, Zr or Hf; and X isan activatable ligand. In an embodiment of the invention, thephosphinimine catalyst has the formula:(1,2-(R*)(C₆F₅)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbyl group having1 to 20 carbon atoms; M is Ti, Zr or Hf; and X is an activatable ligand.In an embodiment of the invention, the phosphinimine catalyst has theformula: (1,2-(n-R*)(C₆F₅)Cp)M(N═P(t-Bu)₃)X₂ where R* is a straightchain alkyl group; M is Ti, Zr or Hf; and X is an activatable ligand. Infurther embodiments, M is Ti and R* is selected from the groupconsisting of n-propyl, n-butyl and n-hexyl, and X is selected fromchloride or methide. In further embodiments, M is Ti and R* is any oneof a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, andn-octyl group. In further embodiments, X is chloride or methide.

The term “perfluorinated aryl group” means that each hydrogen atomattached to a carbon atom in an aryl group has been replaced with afluorine atom as is well understood in the art (e.g. a perfluorinatedphenyl group or substituent has the formula —C₆F₅). In embodiments ofthe invention, Ar—F is selected from the group comprising perfluorinatedphenyl or perfluorinated naphthyl groups.

Some phosphinimine catalysts which may be used in the present inventioninclude: ((C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂;(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂,(1,2-(n-butyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ and(1,2-(n-hexyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂.

In an embodiment of the invention, the phosphinimine catalyst will havea single or multiply substituted indenyl ligand and a phosphinimineligand which is substituted by three tertiary butyl substituents.

An indenyl ligand (or “Ind” for short) as defined in the presentinvention will have framework carbon atoms with the numbering schemeprovided below, so the location of a substituent can be readilyidentified.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand and a phosphinimine ligand which issubstituted by three tertiary butyl substituents.

In an embodiment of the invention, the phosphinimine catalyst will havea singly or multiply substituted indenyl ligand where the substituent isselected from the group consisting of a substituted or unsubstitutedalkyl group, a substituted or an unsubstituted aryl group, and asubstituted or unsubstituted benzyl (e.g. C₆H₅CH₂—) group. Suitablesubstituents for the alkyl, aryl or benzyl group may be selected fromthe group consisting of alkyl groups, aryl groups, alkoxy groups,aryloxy groups, alkylaryl groups (e.g. a benzyl group), arylalkyl groupsand halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, R^(¥)-Indenyl, where the R^(¥)substituent is a substituted or unsubstituted alkyl group, a substitutedor an unsubstituted aryl group, or a substituted or unsubstituted benzylgroup. Suitable substituents for an R^(¥) alkyl, R^(¥) aryl or R^(¥)benzyl group may be selected from the group consisting of alkyl groups,aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (e.g. abenzyl group), arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havean indenyl ligand having at least a 1-position substituent (1-R^(¥))where the substituent R^(¥) is a substituted or unsubstituted alkylgroup, a substituted or an unsubstituted aryl group, or a substituted orunsubstituted benzyl group. Suitable substituents for an R^(¥) alkyl,R^(¥) aryl or R^(¥) benzyl group may be selected from the groupconsisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups,alkylaryl groups (e.g. a benzyl group), arylalkyl groups and halidegroups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl where thesubstituent R^(¥) is in the 1-position of the indenyl ligand and is asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, or a substituted or an unsubstituted benzyl group. Suitablesubstituents for an R^(¥) alkyl, R^(¥) aryl or R^(¥) benzyl group may beselected from the group consisting of alkyl groups, aryl groups, alkoxygroups, aryloxy groups, alkylaryl groups (e.g. a benzyl group),arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a (partially/fully) halide substituted alkyl group,a (partially/fully) halide substituted benzyl group, or a(partially/fully) halide substituted aryl group.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a (partially/fully) halide substituted benzylgroup.

When present on an indenyl ligand, a benzyl group can be partially orfully substituted by halide atoms, preferably fluoride atoms. The arylgroup of the benzyl group may be a perfluorinated aryl group, a 2,6(i.e. ortho) fluoro substituted phenyl group, 2,4,6 (i.e. ortho/para)fluoro substituted phenyl group or a 2,3,5,6 (i.e. ortho/meta) fluorosubstituted phenyl group respectively. The benzyl group is, in anembodiment of the invention, located at the 1 position of the indenylligand.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a pentafluorobenzyl(C₆F₅CH₂—) group.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is a substituted orunsubstituted alkyl group, a substituted or an unsubstituted aryl group,or a substituted or unsubstituted benzyl group, wherein substituents forthe alkyl, aryl or benzyl group are selected from the group consistingof alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halidesubstituents; M is Ti, Zr or Hf; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one fluoride atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one halide atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))Ti(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one fluoride atom; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂-Ind)M(N═P(t-Bu)₃)X₂, where M is Ti, Zr or Hf; and Xis an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂—Ind)Ti(N═P(t-Bu)₃)X₂, where X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂—Ind)Ti(N═P(t-Bu)₃)Cl₂.

The Cocatalyst

In the present invention, the phosphinimine catalyst is used incombination with at least one activator (or “cocatalyst”) to form anactive polymerization catalyst system for olefin polymerization.Activators (i.e. cocatalysts) include ionic activator cocatalysts andhydrocarbyl aluminoxane cocatalysts.

The activator used to activate the phosphinimine catalyst can be anysuitable activator including one or more activators selected from thegroup consisting of alkylaluminoxanes and ionic activators, optionallytogether with an alkylating agent.

The alkylaluminoxanes are complex aluminum compounds of the formula:

R³ ₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂, wherein each R³ is independently selectedfrom the group consisting of C₁₋₂₀ hydrocarbyl radicals and m is from 3to 50. Optionally a hindered phenol can be added to the alkylaluminoxaneto provide a molar ratio of Al¹:hindered phenol of from 2:1 to 5:1 whenthe hindered phenol is present.

In an embodiment of the invention, R³ of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

The alkylaluminoxanes are typically used in substantial molar excesscompared to the amount of group 4 transition metal in the phosphiniminecatalyst. The Al¹:group 4 transition metal molar ratios are from 10:1 to10,000:1, preferably about 30:1 to 500:1.

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneactivator is often used in combination with activatable ligands such ashalogens.

Alternatively, the activator of the present invention may be acombination of an alkylating agent (which may also serve as a scavenger)with an activator capable of ionizing the group 4 metal of thephosphinimine catalyst (i.e. an ionic activator). In this context, theactivator can be chosen from one or more alkylaluminoxane and/or anionic activator.

When present, the alkylating agent may be selected from the groupconsisting of (R⁴)_(p)MgX² _(2-p) wherein X² is a halide and each R⁴ isindependently selected from the group consisting of C₁₋₁₀ alkyl radicalsand p is 1 or 2; R⁴Li wherein in R⁴ is as defined above, (R⁴)_(q)ZnX²_(2-q) wherein R⁴ is as defined above, X² is halogen and q is 1 or 2;(R⁴)_(s)Al²X² _(3-s) wherein R⁴ is as defined above, X² is halogen and sis an integer from 1 to 3. Preferably in the above compounds R⁴ is aC₁₋₄ alkyl radical, and X² is chlorine. Commercially available compoundsinclude triethyl aluminum (TEAL), diethyl aluminum chloride (DEAC),dibutyl magnesium ((Bu)₂Mg), and butyl ethyl magnesium (BuEtMg orBuMgEt).

The ionic activator may be selected from the group consisting of: (i)compounds of the formula [R⁵]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, R⁵ isa cyclic C₅₋₇ aromatic cation or a triphenyl methyl cation and each R⁶is independently selected from the group consisting of phenyl radicalswhich are unsubstituted or substituted with from 3 to 5 substituentsselected from the group consisting of a fluorine atom, a C₁₋₄ alkyl oralkoxy radical which is unsubstituted or substituted by a fluorine atom;and a silyl radical of the formula —Si—(R⁷)₃; wherein each R⁷ isindependently selected from the group consisting of a hydrogen atom anda C₁₋₄ alkyl radical; and (ii) compounds of the formula[(R⁸)_(t)ZH]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, H is a hydrogen atom,Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R⁸ is selectedfrom the group consisting of C₁₋₈ alkyl radicals, a phenyl radical whichis unsubstituted or substituted by up to three C₁₋₄ alkyl radicals, orone R⁸ taken together with a nitrogen atom may form an anilinium radicaland R⁶ is as defined above; and (iii) compounds of the formula B(R⁶)₃wherein R⁶ is as defined above.

In the above compounds preferably R⁶ is a pentafluorophenyl radical, andR⁵ is a triphenylmethyl cation, Z is a nitrogen atom and R⁸ is a C₁₋₄alkyl radical or one R⁸ taken together with a nitrogen atom forms ananilinium radical (e.g. PhR⁸ ₂NH⁺, which is substituted by two R⁸radicals such as for example two C₁₋₄ alkyl radicals).

Examples of compounds capable of ionizing the phosphinimine catalystinclude the following compounds: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra)phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumphenyltris-pentafluorophenyl borate, triphenylmethyliumphenyltrispentafluorophenyl borate, benzene(diazonium)phenyltrispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, trophenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5-tetrafluorophenyl)borate.

Commercially available activators which are capable of ionizing thegroup 4 metal of the phosphinimine catalyst include:

N,N-dimethylaniliniumtetrakispentafluorophenyl borate(“[Me₂NHPh][B(C₆F₅)₄]”); triphenylmethylium tetrakispentafluorophenylborate (“[Ph₃C][B(C₆F₅)₄]”); and trispentafluorophenyl boron and MAO(methylaluminoxane) and MMAO (modified methylaluminoxane).

The ionic activators compounds may be used in amounts which provide amolar ratio of group 4 transition metal to boron that will be from 1:1to 1:6.

Optionally, mixtures of alkylaluminoxanes and ionic activators can beused as activators in the polymerization catalyst.

The Inert Support

In the present invention, the phosphinimine catalyst is supported on aninert support. The support used in the present invention can be anysupport known in the art to be suitable for use with polymerizationcatalysts. For example the support can be any porous or non-poroussupport material, such as talc, inorganic oxides, inorganic chlorides,aluminophosphates (i.e. AlPO₄) and polymer supports (e.g. polystyrene,etc). Preferred supports include Group 2, 3, 4, 5, 13 and 14 metaloxides generally, silica, alumina, silica-alumina, magnesium oxide,magnesium chloride, zirconia, titania, clay (e.g. montmorillonite) andmixtures thereof.

Agglomerate supports such as agglomerates of silica and clay may also beused as a support in the current invention.

Supports are generally used in calcined form. An inorganic oxidesupport, for example, will contain acidic surface hydroxyl groups whichwill react with a polymerization catalyst. Prior to use, the inorganicoxide may be dehydrated to remove water and to reduce the concentrationof surface hydroxyl groups. Calcination or dehydration of a support iswell known in the art. In embodiments of the invention, the support iscalcined at temperatures above 200° C., or above 300° C., or above, 400°C., or above 500° C. In other embodiments, the support is calcined atfrom about 500° C. to about 1000° C., or from about 600° C. to about900° C. The resulting support may be free of adsorbed water and may havea surface hydroxyl content from about 0.1 to 5 mmol/g of support, orfrom 0.5 to 3 mmol/g. The amount of hydroxyl groups in a silica supportmay be determined according to the method disclosed by J. B. Peri and A.L. Hensley Jr., in J. Phys. Chem., 72 (8), 1968, pg 2926.

The support material, especially an inorganic oxide, such as silica,typically has a surface area of from about 10 to about 700 m²/g, a porevolume in the range from about 0.1 to about 4.0 cc/g and an averageparticle size of from about 5 to about 500 μm. In a specific embodiment,the support material has a surface area of from about 50 to about 500m²/g, a pore volume in the range from about 0.5 to about 3.5 cc/g and anaverage particle size of from about 10 to about 200 μm. In anotherspecific embodiment the support material has a surface area of fromabout 100 to about 400 m²/g, a pore volume in the range from about 0.8to about 3.0 cc/g and an average particle size of from about 5 to about100 μm.

The support material, especially an inorganic oxide, such as silica,typically has an average pore size (i.e. pore diameter) of from about 10to about 1000 Angstroms(Å). In a specific embodiment, the supportmaterial has an average pore size of from about 50 to about 500 Å. Inanother specific embodiment, the support material has an average poresize of from about 75 to about 350 Å.

The surface area and pore volume of a support may be determined bynitrogen adsorption according to B.E.T. techniques, which are well knownin the art and are described in the Journal of the American ChemicalSociety, 1938, v 60, pg 309-319.

A silica support which is suitable for use in the present invention hasa high surface area and is amorphous. By way of example, useful silicasare commercially available under the trademark of Sylopol® 958, 955 and2408 from Davison Catalysts, a Division of W. R. Grace and Company andES-70W by PQ Corporation.

Agglomerate supports comprising a clay mineral and an inorganic oxide,may be prepared using a number techniques well known in the artincluding pelletizing, extrusion, drying or precipitation, spray-drying,shaping into beads in a rotating coating drum, and the like. Anodulization technique may also be used. Methods to make agglomeratesupports comprising a clay mineral and an inorganic oxide includespray-drying a slurry of a clay mineral and an inorganic oxide. Methodsto make agglomerate supports comprising a clay mineral and an inorganicoxide are disclosed in U.S. Pat. Nos. 6,686,306; 6,399,535; 6,734,131;6,559,090 and 6,968,375.

An agglomerate of clay and inorganic oxide which may be useful in thecurrent invention may have the following properties: a surface area offrom about 20 to about 800 m²/g, preferably from 50 to about 600 m²/g;particles with a bulk density of from about 0.15 to about 1 g/ml,preferably from about 0.20 to about 0.75 g/ml; an average pore diameterof from about 30 to about 300 Angstroms (Å), preferably from about 60 toabout 150 Å; a total pore volume of from about 0.10 to about 2.0 cc/g,preferably from about 0.5 to about 1.8 cc/g; and an average particlesize of from about 4 to 150 microns (μm), preferably from about 8 to 100microns.

Optionally, a support, for example a silica support, may be treated withone or more salts of the type: Zr(SO₄)₂.4H₂O, ZrO(NO₃)₂, and Fe(NO₃)₃ astaught in CA Patent Application No. 2,716,772 to the same applicant.Supports that have been otherwise chemically treated are alsocontemplated for use with the catalysts and processes of the presentinvention.

Without wishing to be bound by theory, Zr(SO₄)₂.4H₂O and ZrO(NO₃)₂ mayeach act as a source of zirconium oxide (i.e. ZrO₂) which may form forexample after calcinations temperatures are employed. Alternately, theZr(SO₄)₂.4H₂O can be used to add Zr(SO₄)₂ to an inert support ifsuitably high calcinations temperatures (those which promote formationof zirconium oxide) are not employed.

The present invention is not limited to any particular procedure forsupporting the phosphinimine catalyst or the cocatalyst. Processes fordepositing a phosphinimine catalyst complex and/or a cocatalyst on asupport are well known in the art (for some non-limiting examples ofcatalyst supporting methods, see “Supported Catalysts” by James H. Clarkand Duncan J. Macquarrie, published online Nov. 15, 2002 in theKirk-Othmer Encyclopedia of Chemical Technology Copyright © 2001 by JohnWiley & Sons, Inc.; for some non-limiting methods to support a singlesite catalyst see U.S. Pat. No. 5,965,677). For example, thephosphinimine catalyst may be added to a support by co-precipitationwith the support material. The cocatalyst can be added to a supportbefore and/or after the phosphinimine catalyst or together with thephosphinimine catalyst (i.e. the phosphinimine catalyst may be mixedwith a cocatalyst in a suitable solvent or diluents and the mixtureadded to a support). Optionally, the cocatalyst can be added to asupported phosphinimine catalyst in situ or on route to a reactor. Thephosphinimine catalyst and/or cocatalyst may be slurried or dissolved ina suitable diluent or solvent respectively and then added to a support.Suitable solvents or diluents include but are not limited tohydrocarbons and mineral oil. The phosphinimine catalyst may be added tothe solid support, in the form of a solid, solution or slurry, followedby the addition of the cocatalyst in solid form or as a solution orslurry. The cocatalyst may be added to the solid support, in the form ofa solid, solution or slurry, followed by the addition of thephosphinimine catalyst in solid form or as a solution or slurry.Phosphinimine catalyst, cocatalyst, and support can be mixed together inthe presence or absence of a diluent or solvent, but use of diluent(s)or solvent(s) is preferred.

The loading of the phosphinimine catalyst on the support is notspecifically defined, but by way of non-limiting example can be fromabout 0.005 to 1.0, or from about 0.010 to 0.50, or from about 0.015 to0.40, or from about 0.015 to 0.035 mmol of the phosphinimine catalystper gram of support. In further embodiments of the invention, theloading of the phosphinimine catalyst on the support may be from about0.020 to 0.031 mmol, or from about 0.025 to 0.0305 mmol of thephosphinimine catalyst per gram of support.

In embodiments of the invention, a titanium based phosphinimine catalystwill be added to the inert support so as to give from 0.01 to 10 wt % ofTi, or from 0.05 to 5.0 wt % of Ti, or from 0.05 to 3.0 wt % of Ti, orfrom 0.10 to 2.0 wt % of Ti based on the combined weight of thephosphinimine catalyst, the inert support and the cocatalyst.

The phosphinimine based (olefin) polymerization catalyst may be fed to areactor system in a number of ways. The polymerization catalyst may befed to a reactor in dry mode using a dry catalyst feeder, examples ofwhich are well known in the art. Alternatively, the polymerizationcatalyst may be fed to a reactor as a slurry in a suitable diluent.Suitable solvents or diluents are inert hydrocarbons well known topersons skilled in the art and generally include aromatics, paraffins,and cycloparaffinics such as for example benzene, toluene, xylene,cyclohexane, fuel oil, isobutane, mineral oil, kerosene and the like.Further specific examples include but are not limited to hexane,heptanes, isopentane and mixtures thereof. Solvents which will notextract appreciable amounts of the phosphinimine catalyst, thecocatalyst or the catalyst modifier away from the inert support arepreferred. The (olefin) polymerization catalyst components, whichinclude at least one phosphinimine catalyst, at least one support, atleast one cocatalyst, and at least one catalyst modifier, may becombined offline and prior to their addition to a polymerization zone,or they may be combined on route to a polymerization zone.

The Polymerization Process

Olefin polymerization processes which are compatible with the currentinvention include gas phase and slurry phase polymerization processes,with gas phase processes being preferred. Preferably, ethylenecopolymerization with an alpha-olefin is carried out in the gas phase,in for example a fluidized bed reactor.

Detailed descriptions of slurry polymerization processes are widelyreported in the patent literature. For example, particle formpolymerization, or a slurry process where the temperature is kept belowthe temperature at which the polymer goes into solution is described inU.S. Pat. No. 3,248,179. Slurry processes include those employing a loopreactor and those utilizing a single stirred reactor or a plurality ofstirred reactors in series, parallel, or combinations thereof.Non-limiting examples of slurry processes include continuous loop orstirred tank processes. Further examples of slurry processes aredescribed in U.S. Pat. No. 4,613,484.

Slurry processes are conducted in the presence of a hydrocarbon diluentsuch as an alkane (including isoalkanes), an aromatic or a cycloalkane.The diluent may also be the alpha olefin comonomer used incopolymerizations. Alkane diluents include propane, butanes, (i.e.normal butane and/or isobutane), pentanes, hexanes, heptanes andoctanes. The monomers may be soluble in (or miscible with) the diluent,but the polymer is not (under polymerization conditions). Thepolymerization temperature is preferably from about 5° C. to about 200°C., most preferably less than about 120° C. typically from about 10° C.to 100° C. The reaction temperature is selected so that an ethylenecopolymer is produced in the form of solid particles. The reactionpressure is influenced by the choice of diluent and reactiontemperature. For example, pressures may range from 15 to 45 atmospheres(about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane isused as diluent (see, for example, U.S. Pat. No. 4,325,849) toapproximately twice that (i.e. from 30 to 90 atmospheres—about 440 to1300 psi or about 3000-9100 kPa) when propane is used (see U.S. Pat. No.5,684,097). The pressure in a slurry process must be kept sufficientlyhigh to keep at least part of the ethylene monomer in the liquid phase.The reaction typically takes place in a jacketed closed loop reactorhaving an internal stirrer (e.g. an impeller) and at least one settlingleg. Catalyst, monomers and diluents are fed to the reactor as liquidsor suspensions. The slurry circulates through the reactor and the jacketis used to control the temperature of the reactor. Through a series oflet down valves the slurry enters a settling leg and then is let down inpressure to flash the diluent and unreacted monomers and recover thepolymer generally in a cyclone. The diluent and unreacted monomers arerecovered and recycled back to the reactor.

A gas phase process is commonly carried out in a fluidized bed reactor.Such gas phase processes are widely described in the literature (see forexample U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036;5,352,749; 5,405,922; 5,436,304; 5,433,471; 5,462,999; 5,616,661 and5,668,228). In general, a fluidized bed gas phase polymerization reactoremploys a “bed” of polymer and catalyst which is fluidized by a flow ofmonomer and other optional components which are at least partiallygaseous. Heat is generated by the enthalpy of polymerization of themonomer (and optional comonomer(s)) flowing through the bed. Un-reactedmonomer and other optional gaseous components exit the fluidized bed andare contacted with a cooling system to remove this heat. The cooled gasstream, including monomer, and optional other components (such ascondensable liquids), is then re-circulated through the polymerizationzone, together with “make-up” monomer to replace that which waspolymerized on the previous pass. Simultaneously, polymer product iswithdrawn from the reactor. As will be appreciated by those skilled inthe art, the “fluidized” nature of the polymerization bed helps toevenly distribute/mix the heat of reaction and thereby minimize theformation of localized temperature gradients.

The reactor pressure in a gas phase process may vary from aboutatmospheric to about 600 Psig. In another embodiment, the pressure canrange from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In yetanother embodiment, the pressure can range from about 200 psig (1379kPa) to about 400 psig (2759 kPa). In still another embodiment, thepressure can range from about 250 psig (1724 kPa) to about 350 psig(2414 kPa).

The reactor temperature in a gas phase process may vary according to theheat of polymerization as described above. In a specific embodiment, thereactor temperature can be from about 30° C. to about 130° C. In anotherspecific embodiment, the reactor temperature can be from about 60° C. toabout 120° C. In yet another specific embodiment, the reactortemperature can be from about 70° C. to about 110° C. In still yetanother specific embodiment, the temperature of a gas phase process canbe from about 70° C. to about 100° C.

The fluidized bed process described above is well adapted for thepreparation of polyethylene and polyethylene copolymers. Hence, monomersand comonomers include ethylene and C₃₋₁₂ alpha olefins which areunsubstituted or substituted by up to two C₁₋₆ hydrocarbyl radicals;C₈₋₁₂ vinyl aromatic olefins which are unsubstituted or substituted byup to two substituents selected from the group consisting of C₁₋₄hydrocarbyl radicals; and C₄₋₁₂ straight chained or cyclic diolefinswhich are unsubstituted or substituted by a C₁₋₄ hydrocarbyl radical.Illustrative non-limiting examples of alpha-olefins that may becopolymerized with ethylene include one or more of propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene,styrene, alpha methyl styrene, p-t-butyl styrene, and theconstrained-ring cyclic olefins such as cyclobutene, cyclopentene,dicyclopentadiene norbornene, hydrocarbyl-substituted norbornenes,alkenyl-substituted norbornenes and the like (e.g.5-methylene-2-norbornene and 5-ethylidene-2-norbornene,bicyclo-(2,2,1)-hepta-2,5-diene).

In an embodiment, the invention is directed toward a polymerizationprocess involving the polymerization of one or more of the monomer(s)and comonomer(s) including ethylene alone or in combination with one ormore linear or branched comonomer(s) having from 3 to 30 carbon atoms,preferably 3-12 carbon atoms, more preferably 4 to 8 carbon atoms. Theprocess is particularly well suited to copolymerization reactionsinvolving polymerization of ethylene in combination with one or more ofthe comonomers, for example, the alpha-olefins: propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, styrene andcyclic and polycyclic olefins such as cyclopentene, norbornene andcyclohexene or a combination thereof. Other comonomers for use withethylene can include polar vinyl monomers, diolefins such as1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,norbornadiene, and other unsaturated monomers including acetylene andaldehyde monomers. Higher alpha-olefins and polyenes or macromers can beused also. Preferably the comonomer is an alpha-olefin having from 3 to15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4to 10 carbon atoms.

In an embodiment of the present invention, ethylene is copolymerizedwith an alpha olefin having from 3-10 carbon atoms and ethylene makes upat least 75 wt % of the total olefin feed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith an alpha olefin having from 3-10 carbon atoms and ethylene makes upat least 85 wt % of the total olefin feed entering the reactor.

In embodiments of the present invention, ethylene is copolymerized withpropylene, 1-butene, 1-hexene or 1-octene.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-butene and ethylene makes up at least 75 weight % (i.e. wt %) ofthe total olefin feed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-hexene and ethylene makes up at least 75 wt % of the total olefinfeed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-hexene and ethylene makes up at least 85 wt % of the total olefinfeed entering the reactor.

Gas phase fluidized bed polymerization processes may employ a polymerseed bed in the reactor prior to initiating the polymerization process.It is contemplated by the current invention to use a polymer seed bedthat has been treated with a catalyst modifier or an optional scavenger(see below). In addition, the polymer products obtained by using thecatalysts and processes of the current invention may themselves be usedas polymer seed bed materials.

Optional Scavenger

Optionally, scavengers are added to the polymerization process. Thepresent invention can be carried out in the presence of any suitablescavenger or scavengers. Scavengers are well known in the art.

In an embodiment of the invention, scavengers are organoaluminumcompounds having the formula: Al³(X³)_(n)(X⁴)_(3-n), where (X³) is ahydrocarbyl having from 1 to about 20 carbon atoms; (X⁴) is selectedfrom alkoxide or aryloxide, any one of which having from 1 to about 20carbon atoms; halide; or hydride; and n is a number from 1 to 3,inclusive; or hydrocarbyl aluminoxanes having the formula: R³₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂

wherein each R³ is independently selected from the group consisting ofC₁₋₂₀ hydrocarbyl radicals and m is from 3 to 50. Some non-limitingpreferred scavengers useful in the current invention includetriisobutylaluminum, triethylaluminum, trimethylaluminum or othertrihydrocarbyl aluminum compounds.

The scavenger may be used in any suitable amount but by way ofnon-limiting examples only, can be present in an amount to provide amolar ratio of Al:M (where M is the metal of the phosphinimine catalyst)of from about 20 to about 2000, or from about 50 to about 1000, or fromabout 100 to about 500. Generally the scavenger is added to the reactorprior to the polymerization catalyst and in the absence of additionalpoisons and over time declines to 0, or is added continuously.

Optionally, the scavengers may be independently supported. For example,an inorganic oxide that has been treated with an organoaluminum compoundor hydrocarbyl aluminoxane may be added to the polymerization reactor.The method of addition of the organoaluminum or hydrocarbyl aluminoxanecompounds to the support is not specifically defined and is carried outby procedures well known in the art.

A scavenger may optionally be added to the catalyst modifier prior toinclusion of the catalyst modifier in a polymerization catalyst or priorto the combination of a catalyst modifier with another polymerizationcatalyst component (i.e. one or more of the phosphinimine catalyst, theinert support, or the cocatalyst).

Polymer

The polymer compositions made using the present invention are mostpreferably copolymers of ethylene and an alpha olefin selected from1-butene, 1-hexene and 1-octene.

In embodiments of the invention, the copolymer composition will compriseat least 75 weight % of ethylene units, or at least 80 wt % of ethyleneunits, or at least 85 wt % of ethylene units with the balance being analpha-olefin unit, based on the weight of the copolymer composition.

Polymer properties such as average molecular weight (e.g. Mw, Mn andMz), molecular weight distribution (i.e. Mw/Mn), density, melt indices(e.g. I₂, I₅, I₂₁, I₁₀), melt index or melt flow ratios (e.g. I₂₁/I₂,I₂₁/I₅), comonomer distribution breadth index (CDBI), TREF-profile,comonomer distribution profile, and the like as these terms are definedfurther below and in for example co-pending CA Application No. 2,734,167(to the same Applicant) are not specifically defined, but by way ofnon-limiting example only, the polymer compositions made using thepresent invention, may have a density of from 0.910 g/cc to 0.93 g/cc, amelt index of from 0.5 to 10.0 g/10 min, a melt flow ratio (I₂₁/I₂) offrom 14 to 18, a weight average molecular weight of from 40,000 to140,000, and a unimodal or bimodal TREF profile.

Catalyst Modifier Addition

In the present invention, the catalyst modifier affects at least one ofthe following: reactor static level, catalyst static level, reactortemperature control, catalyst productivity, copolymer compositiondistribution, and film gel count.

In an embodiment of the present invention, adding a catalyst modifier toan inert support, prior to the addition of a phosphinimine catalyst andprior to the addition of a cocatalyst during the preparation of apolymerization catalyst, affects the rate at which the polymerizationcatalyst can be fed to a reactor.

In an embodiment of the present invention, adding a catalyst modifier toan inert support, prior to the addition of a phosphinimine catalyst andprior to the addition of a cocatalyst during the preparation of apolymerization catalyst, improves the catalyst flowability as indicatedby a Flodex value.

Use of a specific amount of the catalyst modifier (e.g. from about 0.5to about 4.0 wt % based on the weight of the polymerization catalyst)actually improves the catalyst productivity as is further taught below.

In the present invention, the catalyst modifier may be included in thepolymerization catalyst at any point during the preparation of thepolymerization catalyst so long as the catalyst modifier is added beforethe polymerization catalyst enters a polymerization zone orpolymerization reactor. Hence, in an embodiment of the invention, atleast one phosphinimine catalyst, at least one inert support, at leastone cocatalyst and at least one catalyst modifier are combined in anyorder prior to or on route to their entry into a polymerization zone orreactor. In specific embodiments of the invention: the catalyst modifiermay be added to a support after both the phosphinimine catalyst and thecocatalyst have been added; the catalyst modifier may be added to asupport before either of the phosphinimine catalyst or the cocatalystare added; the catalyst modifier may be added to a support after thephosphinimine catalyst but before the cocatalyst; the catalyst modifiermay be added to a support after the cocatalyst but before thephosphinimine catalyst. Also, the catalyst modifier can be added inportions during any stage of the preparation of the polymerizationcatalyst.

In an embodiment of the present invention, the catalyst modifier isadded to a “finished” polymerization catalyst already comprising thephosphinimine catalyst, inert support and cocatalyst (as used here, theterm “finished” is meant to denote that the catalyst modifier is not yetpresent in the polymerization catalyst). The catalyst modifier can beadded to the “finished” polymerization catalyst offline and prior toaddition of the polymerization catalyst to the polymerization zone, orthe catalyst modifier may be added to the “finished” polymerizationcatalyst on route to a reactor.

In an embodiment of the present invention, the catalyst modifier isadded to an inert support, prior to the addition of the phosphiniminecatalyst and prior to the addition of the cocatalyst to prepare thepolymerization catalyst.

The catalyst modifier may be included in the polymerization catalyst (orwhere appropriate, added to a polymerization catalyst component orcomponents which comprise at least one of the phosphinimine catalyst,the inert support and the cocatalyst) in any suitable manner. By way ofnon-limiting example, the catalyst modifier may be dry blended (if it isa solid) with a “finished” polymerization catalyst (or a polymerizationcatalyst component) or it may be added neat (if the catalyst modifier isa liquid) or it may be added as solution or slurry in a suitablehydrocarbon solvent or diluent respectively. The “finished”polymerization catalyst (or polymerization catalyst components) canlikewise be put into solution or made into a slurry using suitablesolvents or diluents respectively, followed by addition of the catalystmodifier (as a neat solid or liquid or as a solution or a slurry insuitable solvents or diluents) or vice versa. Alternatively, thecatalyst modifier may be deposited onto a separate support and theresulting supported catalyst modifier blended either dry or in a slurrywith the “finished” polymerization catalyst, but this method is notpreferred. The catalyst modifier can be combined neat (if a liquid) oras a solution or slurry in a suitable hydrocarbon solvent or diluentwith an inert support prior to the addition of a phosphinimine catalystand/or a cocatalyst. The catalyst modifier may also be dry blended (ifit is a solid) with an inert support prior to addition of thephosphinimine catalyst and/or the cocatalyst.

Suitable solvents or diluents are inert hydrocarbons and include but arenot limited to aromatics, paraffins, and cycloparaffinics such as forexample benzene, toluene, xylene, cyclohexane, fuel oil, isobutane,mineral oil, kerosene and the like. Further specific examples includebut are not limited to hexane, heptanes, isopentane, cyclohexane,toluene and mixtures thereof.

Removal of diluents or solvents to give the polymerization catalyst as asolid or powder can be carried out using any suitable means known in theart. For example, the catalyst may be isolated by one or more filtrationor decantation steps, or one or more evaporation steps. Removal ofdiluents or solvents by evaporation/drying is well known, but preferablythe evaporation is carried out under conditions which do not adverselyaffect the performance of the polymerization catalyst. Removal ofsolvent or diluents can be carried out under ambient pressures orreduced pressures. Removal of diluents or solvents can be achieved underambient temperatures or elevated temperatures, provided that elevatedtemperatures do not lead to catalyst deactivation. Diluents or solventsmay in some circumstances (i.e. for low boiling diluents/solvents) be“blown off” using an inert gas. The time required to remove the diluentsor solvents is not specifically defined.

Polymerization catalysts in the form of a solid can be fed to apolymerization zone using well known solid catalyst feeder equipment.Alternatively, the polymerization catalyst may be used in slurried form.By “slurried form” it is meant that the polymerization catalyst issuspended in a suitable diluent or mixture of diluents. Suitablediluents may include but are not limited to cyclohexane, pentane,heptanes, isopentane, mineral oil and mixtures thereof. Preferably, thediluent chosen is one in which little or no extraction of polymerizationcatalyst components from the support occurs. Such a slurry form catalystcan be fed to a polymerization reactor zone using suitable slurry feedequipment which is well known in the art.

The amount of catalyst modifier added to a reactor (or other associatedprocess equipment) is conveniently represented herein as the parts permillion (ppm) of catalyst modifier based on the weight of copolymerproduced.

The amount of catalyst modifier included in a polymerization catalyst isconveniently represented herein as a weight percent (wt %) of thecatalyst modifier based on the combined weight of the phosphiniminecatalyst, the inert support and the cocatalyst. In order to avoid anyambiguity, the phrase “weight of the polymerization catalyst” includesthe weight of the phosphinimine catalyst, the inert support, and thecocatalyst but not the weight of the catalyst modifier.

The total amount of catalyst modifier included in the polymerizationcatalyst can range anywhere from about 0.1 to 10 weight percent (orsmaller ranges within this range) based on the combined weight of thephosphinimine catalyst, the inert support and the cocatalyst. However,to maximize catalyst productivity and reactor operability at the sametime, the amount of catalyst modifier included in the polymerizationcatalyst is preferably from 0.25 to 6.0 weight percent (i.e. wt % basedon the weight of the phosphinimine catalyst, the inert support and thecocatalyst), or from 0.25 to 5.0 weight percent, or from 0.5 to 4.5weight percent, or from 1.0 to 4.5 weight percent, or from 0.75 to 4.0weight percent, or from 0.5 to 4.0 weight percent, or from 0.25 to 4.0weight percent, or from 1.0 to 4.0 weight per cent, or from 0.5 to 3.5weight percent, or from 1.25 to 3.75 weight percent, or from 1.0 to 3.5weight percent, or from 1.5 to 3.5 weight percent, or from 0.75 to 3.75weight percent, or from 0.25 to 3.75 weight percent, or from 0.75 to 3.5weight percent, or from 1.0 to 3.75 weight percent.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifiercomprises a “long chain amine” compound as described above in “TheCatalyst Modifier” section and which is present in from 0.25 to 6.0weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.25 to 6.0 weight percent based on the weight of i),ii) and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is ahydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or ahydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, y is 1when x is 1, y is 2 when x is 0, each n is independently an integer from1 to 30 when y is 2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.25 to 5.0 weight percent based on the weight of i),ii) and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is ahydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or ahydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, y is 1when x is 1, y is 2 when x is 0, each n is independently an integer from1 to 30 when y is 2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises at least onecompound represented by the formula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) whereR¹ is a hydrocarbyl group having anywhere from 5 to 30 carbon atoms, andn and m are integers from 1 to 20.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises at least onecompound represented by the formula: R¹N((CH₂)_(n)OH)₂ where R¹ is ahydrocarbyl group having anywhere from 6 to 30 carbon atoms, and n isindependently an integer from 1-20.

One measure of reactor operability is the level of static present in oneor more locations in a gas phase fluidized bed polymerization system.The level of static present in the polymerization catalyst is also auseful proxy for potential reactor operability problems. The effect ofthe catalyst modifier on static may be conveniently monitored with oneor more static probes. Static probes are designed to register staticactivity above or below zero. In a gas phase polymerization run, afouling event is sometimes preceded by large non-zero measurements ofstatic. One or more static probes can be used to measure the level ofstatic anywhere in the reactor proper (including upper, lower orintermediate bed probes), at a location within the entrainment zone, ata location within the recycle stream, at the distributor plate, at theannular disk which provides access to the flowing stream of gas enteringthe reactor, and the like as discussed in U.S. Pat. Appl. No.2005/0148742A1, which is incorporated herein by reference. Hence, thestatic probes themselves may be designated as at least one recycle lineprobe, at least one annular disk probe, at least one distributor plateprobe, at least one upper reactor static probe, an annular disk probe ora conventional probe which is located within the fluidized bed. Thepolymerization catalyst static can be measured using a static probelocated in the catalyst injection tube, or catalyst metering device.

In a conventional reactor wall static probe, the probe measures theelectric current that flows from a probe tip and which results fromparticle impact therewith. The particles could be resin particles orcatalyst particles for example. The probe measures current per unit ofarea on the probe tip which serves as an estimate of the charge transferoccurring on the reactor wall. In this scenario, the probe tip is meantto simulate a small portion of the reactor wall. The probe tip may bemade of any suitable conducting materials such as carbon steel, iron,stainless steel, titanium, platinum, nickel, Monel®, copper, aluminumand the like as further described in U.S. Pat. No. 6,008,662, which isincorporated herein by reference.

More generally, static probes include a metallic probe tip, one or moresignal wires, and an electric feed to a measuring instrument asdiscussed in U.S. Pat. Appl. 2005/0148742 A1. Any instrument or devicecapable of measuring current flow from the probe tip to ground can beused. These include for example an ammeter, a picoammeter, amulti-meter, or electrometer. The current may also be measured in anindirect way by instead determining the voltage generated by the currentwhen it is passed through an in-series resistor. The current can bedetermined from voltage using Ohm's law as further described in U.S.Pat. No. 6,008,662, which is incorporated herein by reference.

Typical current levels measured with a conventional reactor wall staticprobe range from ±0.1 to 10 nanoamps/cm², or smaller ranges within thisrange (e.g. ±0.1 to 8 nanoamps/cm², ±0.1 to 6 nanoamps/cm² and thelike). The measurements of current will generally be represented asaverages over a given time period or they may be represented as the rootmean squared values in order to provide all positive number values.

Any one or more static probes in any location in the fluidized bedsystem may be determinative of the onset of a reactor discontinuityevent.

The effect of the catalyst modifier on reactor operability may also beevidenced by other observations not limited to that of the measurementof static activity. For example, productivity levels can be measured (ingrams of polymer produced per gram of catalyst used) as an indicator ofoverall reactor and catalyst performance. Activity measurements may besimilarly used (by incorporating a time dimension into productivitymeasurements). Direct or indirect observations of temperaturefluctuations at various locations in a fluidized bed reactor system (orother reactor systems) can also be monitored and the ideal amount ofcatalyst modifier determined in order to minimize heat fluctuations.Common thermocouples can be used at various locations for this purpose.

In an embodiment of the invention, the polymerization process is carriedout by introducing a polymerization catalyst into a reactor, thepolymerization catalyst comprising: i) a phosphinimine catalyst; ii) aninert support; iii) a cocatalyst; and iv) a catalyst modifier; whereinthe catalyst modifier comprises a “long chain amine” compound asdescribed above in “The Catalyst Modifier” section and which is presentin from 0.25 to 6.0 weight percent based on the weight of i), ii) andiii) of the polymerization catalyst.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.25to 6.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization process comprisescontacting ethylene and at least one alpha olefin with a polymerizationcatalyst in a gas phase reactor, the polymerization catalyst comprising:i) a phosphinimine catalyst, ii) an inert support, iii) a cocatalyst,and iv) a catalyst modifier; wherein the catalyst modifier is present infrom 0.25 to 6.0 weight percent based on the weight of i), ii), and iii)of the polymerization catalyst and comprises a compound having theformula:

R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1; and wherein the polymerizationcatalyst is prepared by adding all of the catalyst modifier to the inertsupport prior to the addition of the phosphinimine catalyst and prior tothe addition of the cocatalyst.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.25to 5.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.5to 4.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.0to 4.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.25to 3.75 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.5to 3.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1 to 30 when y is 1.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; improves at least one ofreactor static level (i.e. decreases), catalyst static level (i.e.decreases), reactor temperature excursions (i.e. decreases) and catalystproductivity (i.e. increases), relative to a gas phase polymerizationprocess carried out in a reactor in the presence of a polymerizationcatalyst comprising: i) a phosphinimine catalyst; ii) an inert support;and iii) a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier, wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst; improves at least one ofreactor static level (i.e. decreases), catalyst static level (i.e.decreases), reactor temperature excursions (i.e. decreases) and catalystproductivity (i.e. increases), relative to a gas phase polymerizationprocess carried out in a reactor in the presence of a polymerizationcatalyst comprising: i) a phosphinimine catalyst; ii) an inert support;and iii) a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1; decreases the reactorstatic level relative to a gas phase polymerization process carried outin a reactor in the presence of a polymerization catalyst comprising: i)a phosphinimine catalyst; ii) an inert support; and iii) a cocatalyst,but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1; decreases the catalyststatic level relative to a gas phase polymerization process carried outin a reactor in the presence of a polymerization catalyst comprising: i)a phosphinimine catalyst; ii) an inert support; and iii) a cocatalyst,but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1; decreases the severityof reactor temperature excursions relative to a gas phase polymerizationprocess carried out in a reactor in the presence of a polymerizationcatalyst comprising: i) a phosphinimine catalyst; ii) an inert support;and iii) a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1; has increasedproductivity relative to a gas phase polymerization process carried outin a reactor in the presence of a polymerization catalyst comprising: i)a phosphinimine catalyst; ii) an inert support; and iii) a cocatalyst,but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier; wherein the catalyst modifieris present in from 0.25 to 6.0 weight percent based on the weight of i),ii), and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is ahydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or ahydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0, y is 1when x is 1, y is 2 when x is 0, each n is independently an integer from1 to 30 when y is 2, and n is an integer from 1 to 30 when y is 1; wherethe polymerization catalyst is prepared by adding all of the catalystmodifier to the inert support prior to the addition of the phosphiniminecatalyst and prior to the addition of the cocatalyst; has improvedcatalyst feeding relative to a gas phase polymerization process carriedout in a reactor in the presence of a polymerization catalyst which isprepared by adding all of the catalyst modifier to the inert supportafter the addition of the phosphinimine catalyst and after the additionof the cocatalyst.

The presence of a catalyst modifier in the polymerization catalyst mayalso affect the properties of ethylene copolymers produced during gasphase polymerization of ethylene and an alpha-olefin as well as theproperties of films made with those copolymers.

For example, the catalyst modifier may, when added in appropriateamounts to a phosphinimine based polymerization catalyst, alter thecomposition distribution (as defined below) in an ethylene copolymerrelative to copolymer produced with a phosphinimine based polymerizationcatalyst not treated with the catalyst modifier. The catalyst modifiermay, when added in appropriate amounts to a phosphinimine basedpolymerization catalyst, increase the short chain branching homogeneityof an ethylene copolymer relative to copolymer produced with aphosphinimine based polymerization catalyst not treated with a catalystmodifier. More specifically, a catalyst modifier may, when present inthe polymerization catalyst in appropriate amounts, alter one or more ofthe following: the composition distribution breadth index (CDBI) of theethylene copolymer as measured using temperature rising elutionfractionation (TREF) methods; the weight percent of a higher temperatureeluting material (i.e. from 90° C. to 105° C.) observed in TREF profileobtained for the ethylene copolymer; and the comonomer distributionprofile in the ethylene copolymer as measured by gel permeationchromatography with Fourier transform infra-red detection (GPC-FTIR).

Ethylene copolymers can be defined by a composition distribution breadthindex (CDBI), which is a measure as to how comonomers are distributed inan ethylene copolymer. The definition of composition distributionbreadth index (CDBI) can be found in U.S. Pat. No. 5,206,075 and PCTpublication WO 93/03093. The CDBI is conveniently determined usingtechniques which isolate polymer fractions based on their solubility(and hence their comonomer content). For example, temperature risingelution fractionation (TREF) as described by Wild et al. J. Poly. Sci.,Poly. Phys. Ed. Vol. 20, p 441, 1982 can be employed. From the weightfraction versus composition distribution curve, the CDBI is determinedby establishing the weight percentage of a copolymer sample that has acomonomer content within 50% of the median comonomer content on eachside of the median. Generally, ethylene copolymers with a CDBI of lessthan about 50%, are considered “heterogeneously branched” copolymerswith respect to the short chain branching. Such heterogeneously branchedmaterials may include a highly branched fraction, a medium branchedfraction and a higher density fraction having little or no short chainbranching. In contrast, ethylene copolymers with a CDBI of greater thanabout 50% are considered “homogeneously branched” copolymers withrespect to short chain branching in which the majority of polymer chainsmay have a similar degree of branching.

In embodiments of the invention, an ethylene copolymer made with apolymerization catalyst comprising: i) a phosphinimine catalyst, ii) aninert support, iii) a cocatalyst and iv) from 1.0 to 4.0 wt % of acatalyst modifier (based on the weight of i), ii), and iii) of thepolymerization catalyst); has an at least 3%, or at least 5%, or atleast 7% higher composition distribution breadth index (as measured byTREF) than an ethylene copolymer made with a catalyst comprising: i) aphosphinimine catalyst, ii) an inert support, and iii) a cocatalyst, butno catalyst modifier.

An ethylene copolymer can be defined by a weight percent of a highertemperature eluting material (i.e. from 90° C. to 105° C.) observed inTREF profile. The amount of copolymer which elutes at a temperature offrom 90° C. to 105° C. is another indication as to how comonomers aredistributed in an ethylene copolymer.

In embodiments of the invention, an ethylene copolymer made with apolymerization catalyst comprising i) a phosphinimine catalyst, ii) aninert support, iii) a cocatalyst and iv) from 1.0 to 4.0 wt % of acatalyst modifier (based on the weight of i), ii) and iii) of thepolymerization catalyst) has a weight percent of an ethylene copolymerfraction (based on the weight of the copolymer) which elutes at from 90°C. to 105° C. in a TREF analysis which is decreased by at least 1%, orby at least 2%, or by at least 3% relative to an ethylene copolymer madewith a catalyst comprising: i) a phosphinimine catalyst, ii) an inertsupport, and iii) a cocatalyst, but no catalyst modifier.

Ethylene copolymers can have a number of different comonomerdistribution profiles which represent how the comonomers are distributedamongst polymer chains of different molecular weight. The so called“comonomer distribution profile” is most typically measured usingGel-Permeation Chromatography with Fourier Transform Infra-Red detection(GPC-FTIR). If the comonomer incorporation decreases with molecularweight, as measured using GPC-FTIR, the distribution is described as“normal” or “negative”. If the comonomer incorporation is approximatelyconstant with molecular weight, as measured using GPC-FTIR, thecomonomer distribution is described as “flat”. The terms “reversedcomonomer distribution” and “partially reversed comonomer distribution”mean that in the GPC-FTIR data obtained for the copolymer, there is oneor more higher molecular weight components having a higher comonomerincorporation than in one or more lower molecular weight segments. Ifthe comonomer incorporation rises with molecular weight, thedistribution is described as “reversed”. Where the comonomerincorporation rises with increasing molecular weight and then declines,the comonomer distribution is described as “partially reversed”.

In embodiments of the invention, use of a polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) from 1.0 to 4.0 wt % of a catalyst modifier (basedon the weight of i), ii) and iii) of the polymerization catalyst) forethylene/alpha-olefin copolymerization, changes the comonomerdistribution profile of an ethylene copolymer from a normal profile to aflat profile, or from a flat profile to a reversed profile or from anormal profile to a reversed profile, relative to an ethylene copolymermade with a polymerization catalyst comprising: i) a phosphiniminecatalyst, ii) an inert support, and iii) a cocatalyst, but no catalystmodifier.

The catalyst modifier, may when included in the phosphinimine basedpolymerization catalyst in appropriate amounts, provide ethylenecopolymer which when cast into film has reduced numbers of gels,relative to copolymer produced with a phosphinimine based olefinpolymerization catalyst not treated with a catalyst modifier.

In an embodiment of the invention, the presence of from 1.0 to 4.0weight per cent of a catalyst modifier in a polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier decreases the number of gelspresent (by OCS gel count) in a film cast from a copolymer obtainedusing the polymerization catalyst (relative to film cast from acopolymer obtained using a polymerization catalyst not treated with acatalyst modifier).

In embodiments of the invention, the presence of from 1.0 to 4.0 weightper cent of a catalyst modifier in an olefin polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier, decreases the number of gelspresent in a film cast from a copolymer obtained using the olefinpolymerization catalyst, from above 100 to below 10, or from above 50 tobelow 10, or from above 20 to below 10 according to OCS gel count.

Although a catalyst modifier, must in the present invention, be presentin the polymerization catalyst at some point before adding thepolymerization catalyst to a polymerization zone, the present inventiondoes not preclude embodiments in which a catalyst modifier is also addeddirectly to a reaction zone or to some other part of a gas phase processwhich is associated with the reaction zone.

Hence, the catalyst modifier may also be fed directly to a reactorsystem using any appropriate method known to persons skilled in the art.For example, the catalyst modifier may be fed to a reactor system as aneat solid or liquid or as a solution or as a slurry in a suitablesolvent or diluent respectively. Suitable solvents or diluents are inerthydrocarbons well known to persons skilled in the art and generallyinclude aromatics, paraffins, and cycloparaffinics such as for examplebenzene, toluene, xylene, cyclohexane, fuel oil, isobutane, mineral oil,kerosene and the like. Further specific examples include but are notlimited to hexane, heptanes, isopentane and mixtures thereof.Alternatively, the catalyst modifier may be added to an inert supportmaterial and then fed to a polymerization reactor as a dry feed or aslurry feed. The catalyst modifier may be fed to various locations in areactor system. When considering a fluidized bed process for example,the catalyst modifier may be fed directly to any area of the reactionzone, or any area of the entrainment zone, or it may be fed to any areawithin the recycle loop, where such areas are found to be effectivesites at which to feed a catalyst modifier. For example, furthercatalyst modifier can be added to a reactor with all or a portion of oneor more of the monomers or the cycle gas; or further catalyst modifiercan be added through a dedicated feed line or added to any convenientfeed stream including an ethylene feed stream, a comonomer feed stream,a catalyst feed line or a recycle line; or further catalyst modifier canbe fed to a location in a fluidized bed system in a continuous orintermittent manner; or further catalyst modifier can be added to areactor at a time before, after or during the start of thepolymerization reaction; or further catalyst modifier can be added byspraying a solution or mixture of the catalyst modifier directly into areaction zone; or further catalyst modifier can be added to a polymerseed bed present in a reactor prior to starting the polymerizationreaction by introduction of the polymerization catalyst.

When further catalyst modifier is desired then it may be added as asolution or mixture with a solvent or diluent respectively, and thecatalyst modifier may make up for example from 0.1 to 30 wt % of thesolution or mixture, or from 0.1 to 20 wt %, or from 0.1 to 10 wt %, orfrom 0.1 to 5 wt % or from 0.1 to 2.5 wt % or from 0.2 to 2.0 wt %,although a person skilled in the art will recognize that further,possibly broader ranges, may also be used and so the invention shouldnot be limited in this regard.

When further catalyst modifier is desired then the amount of catalystmodifier fed to a reactor will generally not exceed about 150 ppm, or100 ppm, or 75 ppm, or 50 ppm, or 25 ppm (parts per million based on theweight of the (co)polymer being produced).

EXAMPLES

Catalyst Modifier

Atmer-163™ was obtained from CRODA CANADA LTD and dried over 3 Åmolecular sieves for several days prior to use. Atmer-163 has as itsmain component, a mixture of C13 to C15 hydrocarbyl diethanolamines,CH₃(CH₂)_(n)N(CH₂CH₂OH)₂ where n is 12 to 14.

Armostat-1800™ was obtained from Akzo Nobel and purified by drying atoluene or pentane solution over 3 Å molecular sieves for several daysprior to use. Armostat-1800 is principally a long chain substitutedalkanolamine having the formula: C₁₈H₃₇N(CH₂CH₂OH)₂.

In an alternative manner of drying the Armostat-1800 material, 950 g ofthe material, was loaded in a 2 L-round bottom flask and melted in anoil bath at 80° C. The oil bath temperature was then raised to 110° C.and a high vacuum was applied while maintaining stirring. Bubbles wereobserved due to the release of gas and moisture vapor. Approximately twohours later, gas evolution subsided and heating/evacuation was continuedfor another hour. The Armostat-1800 material was then cooled down toroom temperature and stored under nitrogen atmosphere until use. Themoisture level in the purified Armostat-1800 was determined to be 110ppm by Karl-Fischer titration method.

Polymerization Catalysts

All reactions involving air and or moisture sensitive compounds wereconducted under nitrogen using standard Schlenk and cannula techniques,or in a glovebox. Reaction solvents were purified either using thesystem described by Pangborn et. al. in Organometallics 1996, v 15, p.1518 or used directly after being stored over activated 4 Å molecularsieves. The aluminoxane used was a 10% MAO solution in toluene suppliedby Albemarle which was used as received. The support used was silicaSylopol 2408 obtained from W.R. Grace. & Co. The support was calcined byfluidizing with air at 200° C. for 2 hours followed by nitrogen at 600°C. for 6 hours and stored under nitrogen. The phosphinimine catalystcompound (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ was made in a mannersimilar to the procedure given in U.S. Pat. No. 7,531,602 (see Example2). The phosphinimine compound (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ wasmade as follows. To distilled indene (15.0 g, 129 mmol) in heptane (200mL) was added BuLi (82 mL, 131 mmol, 1.6 M in hexanes) at roomtemperature. The resulting reaction mixture was stirred overnight. Themixture was filtered and the filter cake washed with heptane (3×30 mL)to give indenyllithium (15.62 g, 99% yield). Indenyllithium (6.387 g,52.4 mmol) was added as a solid over 5 minutes to a stirred solution ofC₆F₅CH₂—Br (13.65 g, 52.3 mmol) in toluene (100 mL) at room temperature.The reaction mixture was heated to 50° C. and stirred for 4 h. Theproduct mixture was filtered and washed with toluene (3×20 mL). Thecombined filtrates were evaporated to dryness to afford 1-C₆F₅CH₂-indene(13.58 g, 88%). To a stirred slurry of TiCl₄0.2THF (1.72 g, 5.15 mmol)in toluene (15 mL) was added solid (t-Bu)₃P═N—Li (1.12 g, 5 mmol) atroom temperature. The resulting reaction mixture was heated at 100° C.for 30 min and then allowed to cool to room temperature. This mixturecontaining ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol) was used in the nextreaction. To a THF solution (10 mL) of 1-C₆F₅CH₂-indene (1.48 g, 5 mmol)cooled at −78° C. was added n-butyllithium (3.28 mL, 5 mmol, 1.6 M inhexanes) over 10 minutes. The resulting dark orange solution was stirredfor 20 minutes and then transferred via a double-ended needle to atoluene slurry of ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol). The cooling wasremoved from the reaction mixture which was stirred for a further 30minutes. The solvents were evaporated to afford a yellow pasty residue.The solid was re-dissolved in toluene (70 mL) at 80° C. and filteredhot. The toluene was evaporated to afford pure(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (2.35 g, 74%).

Type 1 Polymerization Catalysts Based on(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (1a) or(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (1b); Comparative: without catalystmodifier present: Type 1a) To a slurry of dehydrated silica (361.46 g)in toluene (1400 mL) was added a 10 wt % MAO solution (1004.41 g of 4.5wt % Al in toluene) over 35 minutes. The vessel containing the MAO wasrinsed with toluene (2×50 mL) and added to the reaction mixture. Theresultant slurry was stirred with an overhead stirrer assembly (200 rpm)for 2 hours at ambient temperature. To this slurry was added a toluene(˜100 mL) solution of (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (8.47 g)over 10 minutes. This solution may need to be gently heated to 45° C.for a brief period (5 minutes) to fully dissolve the molecule. Thevessel containing the molecule was rinsed with toluene (2×10 mL) andadded to the reaction mixture. After stirring for 2 hours (200 rpm) atambient temperature the slurry was filtered, washed with pentane (2×200mL) and dried in vacuo to less than 1.5 wt % residual volatiles. Thesolid catalyst was isolated and stored under nitrogen until further use.Type 1 b) In a glovebox, into a 2 L, three-neck round bottom flaskequipped with an overhead stirrer was added 150 mL toluene. While thesolvent was stirred, 38.894 g of dehydrated silica was added. Next,107.940 g of a MAO in toluene solution containing 4.5 wt % Al was addedinto the flask by cannula over a period of about 15 minutes whilestirring was maintained. The MAO solution container was rinsed twotimes, each with 25 mL toluene and the rinses were added into the flask.The slurry was stirred for 1 hour at room temperature. A solution of0.944 g (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ complex in 10 mL toluenewas then added into the flask over a period of about 10 minutes. Themetal complex solution container was rinsed three times, each with about6 mL toluene and the rinses were added into the flask. The slurry wasstirred for 2 hours at ambient temperature. The catalyst slurry waspoured into a fritted funnel, which was fitted onto a filter flask, andreduced pressure was then applied to the filter flask to separate thereaction solvent. Toluene (25 mL) was added to the filter cake andstirred with a spatula to obtain a well dispersed slurry. Reducedpressure was then applied to the filter flask to remove the washsolvent. A second toluene wash was done and reduced pressure applied toremove solvent. Pentane (50 mL) was added to the filter cake and stirredwith spatula to obtain a well dispersed slurry. Reduced pressure wasthen applied to the filter flask to remove wash solvent. A secondpentane wash was done and reduced pressure applied to remove solventuntil the filter cake appears to be dry. The filter cake was thentransferred to a 1 L round-bottomed flask and the catalyst was dried byapplying reduced pressure to the flask until a pressure of about 300mTorr was obtained.

Type 2 Polymerization Catalysts Based on(1,2-(n-Propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)₂ (2a, 2b, 2c, 2d) or(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (2e); Inventive: with catalystmodifier present: Type 2a) 1.5 wt % Atmer-163. To a pentane (400 mL)slurry of the catalyst prepared as above (100.17 g of Catalyst Type 1a)was added neat Atmer-163 (1.55 g). The slurry was stirred with anoverhead stirrer assembly (200 rpm) for 30 minutes at ambienttemperature at which point volatiles were removed in vacuo while heatingto 30° C. The resultant catalyst was dried to less than 1.5 wt %residual volatiles, isolated and stored under nitrogen until furtheruse. Type 2b) 1.5 wt % Armostat-1800. To a slurry of dehydrated silica(58.54 g) in toluene (240 mL) was added a 10 wt % MAO solution (161.89 gof 4.5 wt % Al in toluene) over 35 minutes. The vessel containing theMAO was rinsed with toluene (2×25 mL) and added to the reaction mixture.The resultant slurry was stirred with an overhead stirrer assembly (200rpm) for 2 hours at ambient temperature. To this slurry was added atoluene (35 mL) solution of (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂(0.91 g) over 10 minutes. This solution may need to be gently heated to45° C. for a brief period (5 minutes) to fully dissolve the molecule.The vessel containing the molecule was rinsed with toluene (2×10 mL) andadded to the reaction mixture. After stirring for 2 hours (200 rpm) atambient temperature a toluene (20 mL) solution of Armostat-1800 (1.37 g)was added to the slurry which was further stirred for 30 minutes. Theslurry was decanted, stirred with pentane (100 mL) for 30 minutes andthen decanted once again. This step was repeated once more before thecatalyst was dried in vacuo to less than 1.5 wt % residual volatiles.The solid catalyst was isolated and stored under nitrogen until furtheruse. Type 2c) 2.5 wt % Armostat-1800. A polymerization catalystcontaining 2.5 wt % of Armostat-1800 was made similarly to Type 2b aboveexcept that the relative amount of Armostat-1800 added was increased togive 2.5 weight per cent of catalyst modifier based on the combinedweight of the phosphinimine catalyst, the support and the cocatalyst.Type 2d) 3.5 wt % Armostat-1800. A polymerization catalyst containing3.5 wt % of Armostat-1800 was made similarly to Type 2b above exceptthat the relative amount of Armostat-1800 added was increased to give3.5 weight per cent of catalyst modifier based on the combined weight ofthe phosphinimine catalyst, the support and the cocatalyst. Type 2e) 2.5wt % Armostat-1800. In a 3 L, three-neck round bottom flask equippedwith an overhead stirrer was added toluene (320 mL). While the stirrerwas maintained at 200 rpm, dehydrated silica (79.702 g) was added. A 10wt % MAO in toluene solution (174.607 g) was added into the flask bycannula over a period of about 15 minutes while stirring was maintained.The MAO solution container was rinsed with toluene (2×25 mL), and therinses were added into the flask. The slurry was stirred for 2 hours atroom temperature. The complex, (1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂,(1.996 g) was then added into the flask in solid form over a period ofabout 5 minutes. The slurry was stirred for 2 hours at ambienttemperature. A 15 wt % Armostat-1800 in toluene solution (16.762 g) wasadded into the flask over a period of 3 minutes. The container wasrinsed with toluene (2×5 mL), and the rinses were added in the flask.The slurry was further stirred at ambient temperature for 30 minutes.The catalyst slurry was poured into a fritted funnel, which was fittedonto a filter flask, and reduced pressure applied to the filter flask toseparate the reaction solvent. Toluene (150 mL) was added to the filtercake and stirred with a spatula to obtain a well dispersed slurry.Reduced pressure was then applied to the filter flask to remove the washsolvent. A second toluene wash was done and reduced pressure applied toremove solvent. Pentane (150 mL) was added to the filter cake andstirred with spatula to obtain a well-dispersed slurry. Reduced pressurewas then applied to the filter flask to remove wash solvent. A secondpentane wash was done and reduced pressure applied to remove solventuntil the filter cake appears to be dry. The filter cake was thentransferred to a 2 L round-bottomed flask and the catalyst was dried byapplying reduced pressure to the flask until 315 mTorr was obtained.

General Polymerization Conditions

Continuous ethylene/1-hexene gas phase copolymerization experiments wereconducted in a 56.4 liter technical scale reactor (TSR) in continuousgas phase operation (for an example of a TSR reactor set up see Eur.Pat. Appl. No. 659,773A1). Ethylene polymerizations were run at 80° C.with a total operating pressure of 300 pounds per square inch gauge(psig). Gas phase compositions for ethylene, 1-hexene and hydrogen werecontrolled via closed-loop process control to values of 35-51, 0.5-1.7and 0.018-0.042 mole percent, respectively. Nitrogen constituted theremainder of the gas phase mixture (approximately 49 mole %). Typicalproduction rate for these conditions was 2.0 to 3.0 kg of polyethyleneper hour. Triethylaluminum (TEAL) was fed to the reactor continuously,as a 0.25 wt % solution in hexane (solution fed at about 10 mL/hr) inorder to scavenge impurities. The residence time in the reactor is heldat 1.5-3.0 hr, with a production rate range from 1.5-2.7 kg/hr.

The catalyst metering device used for administering catalyst to thereactor is equipped with a static probe that measures electrostaticcharge carried by the solid material passing through a monitored tubeleading catalyst to the reactor.

Polymer Analysis

Melt index, I₂, in g/10 min was determined on a Tinius Olsen Plastomer(Model MP993) in accordance with ASTM D1238 condition F at 190° C. witha 2.16 kilogram weight. Melt index, I₁₀, was determined in accordancewith ASTM D1238 condition F at 190° C. with a 10 kilogram weight. Highload melt index, I₂₁, in g/10 min was determined in accordance with ASTMD1238 condition Eat 190° C. with a 21.6 kilogram weight.

Polymer density was determined in grams per cubic centimeter (g/cc)according to ASTM D792.

Molecular weight information (M_(w), M_(n) and M_(z) in g/mol) andmolecular weight distribution (M_(w)/M_(n)), and z-average molecularweight distribution (M_(z)/M_(w)) were analyzed by gel permeationchromatography (GPC), using an instrument sold under the trade name“Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in this solventand were run without filtration. Molecular weights are expressed aspolyethylene equivalents with a relative standard deviation of 2.9% forthe number average molecular weight (“Mn”) and 5.0% for the weightaverage molecular weight (“Mw”). Polymer sample solutions (1 to 2 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourShodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with Cirrus GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

The peak melting point (T_(m)) and percent of crystallinity of thepolymers were determined by using a TA Instrument DSC Q1000 ThermalAnalyser at 10° C./min. In a DSC measurement, a heating-cooling-heatingcycle from room temperature to 200° C. or vice versa was applied to thepolymers to minimize the thermo-mechanical history associated with them.The melting point and percent of crystallinity were determined by theprimary peak temperature and the total area under the DSC curverespectively from the second heating data. The peak melting temperatureT_(m) is the higher temperature peak, when two peaks are presented in abimodal DSC profile (typically also having the greatest peak height).

A compression molded film of 0.0035 inches was extracted at 50° C. inhexane for 2 hours. The sample was re-weighed and the extractablecontent was determined from the relative change in sample weightaccording to ASTM D5227.

The branch frequency of copolymer samples (i.e. the short chainbranching, SCB per 1000 carbons) and the C₆ comonomer content (in wt %)was determined by Fourier Transform Infrared Spectroscopy (FTIR) as perthe ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IRSpectrophotometer equipped with OMNIC version 7.2a software was used forthe measurements.

The determination of branch frequency as a function of molecular weight(and hence the comonomer distribution profile) was carried out usinghigh temperature Gel Permeation Chromatography (GPC) and FT-IR of theeluent. Polyethylene standards with a known branch content, polystyreneand hydrocarbons with a known molecular weight were used forcalibration.

To determine CDBI, a solubility distribution curve is first generatedfor the copolymer. This is accomplished using data acquired from theTREF technique. This solubility distribution curve is a plot of theweight fraction of the copolymer that is solubilized as a function oftemperature. This is converted to a cumulative distribution curve ofweight fraction versus comonomer content, from which the CDBI isdetermined by establishing the weight percentage of a copolymer samplethat has a comonomer content within 50% of the median comonomer contenton each side of the median. The weight percentage of a higher densityfraction, (i.e. the wt % eluting from 90-105° C.), is determined bycalculating the area under the TREF curve at an elution temperature offrom 90 to 105° C. The weight percent of copolymer eluting below 40° C.can be similarly determined. For the purpose of simplifying thecorrelation of composition with elution temperature, all fractions areassumed to have a Mn≧15,000, where Mn is the number average molecularweight of the fraction. Any low molecular weight fractions presentgenerally represent a trivial portion of the polymer. The remainder ofthis description maintains this convention of assuming all fractionshave Mn≧15,000 in the CDBI measurement.

Temperature rising elution fractionation (TREF) method. Polymer samples(50 to 150 mg) were introduced into the reactor vessel of acrystallization-TREF unit (Polymer ChAR™). The reactor vessel was filledwith 20 to 40 ml 1,2,4-trichlorobenzene (TCB), and heated to the desireddissolution temperature (e.g. 150° C.) for 1 to 3 hours. The solution(0.5 to 1.5 ml) was then loaded into the TREF column filled withstainless steel beads. After equilibration at a given stabilizationtemperature (e.g. 110° C.) for 30 to 45 minutes, the polymer solutionwas allowed to crystallize with a temperature drop from thestabilization temperature to 30° C. (0.1 or 0.2° C./minute). Afterequilibrating at 30° C. for 30 minutes, the crystallized sample waseluted with TCB (0.5 or 0.75 mL/minute) with a temperature ramp from 30°C. to the stabilization temperature (0.25 or 1.0° C./minute). The TREFcolumn was cleaned at the end of the run for 30 minutes at thedissolution temperature. The data were processed using Polymer ChARsoftware, Excel spreadsheet and TREF software developed in-house.

The TREF procedure described above is well known to persons skilled inthe art and can be used to determine: the overall TREF profile, CDBI,copolymer wt % below 40° C., and copolymer wt % from 90° C. to 105° C.

Gel Count Procedure

An in-lab OCS gel measurement system, which consists of an OCS gelcamera, FSA 100 film scanning unit, image analysis software, cast lineextruder and chill roll windup setup, is used to determine the amount ofgels in a 1.0 to 2.0 mil cast film. For a gel count measurement, apolymer sample is added into a 20 mm extruder with a mixing screw of 3:1or 4:1 compression ratio and run at 60 rpm. The haul-off speed and chillroll temperature of the cast film line are set at 8.0 m/min and 23 to30° C. respectively. The pictures of cast film are taken by an OCScamera continuously and the film scanning unit with image analysissoftware is used to monitor the gel data in the pictures. The gel countsin a cast film are defined as the total area of defects per total areameasured and reported as a total ppm value.

Polymerization Results

EXAMPLES 1, 3, 5, 6, 13 AND 16 COMPARATIVE BASELINE RUNS

The Type 1 Catalysts (each of the Type 1 Catalysts 1a and 1b, areprepared as described above) were placed under a N2 blanket and using adry catalyst feeder, a small shot of supported catalyst was continuouslyadded to a technical scale reactor via a feeding tube. Equilibriumpolymerization conditions were established after a period of 4 residencetimes. Once equilibrium conditions were established, the static level inthe reactor was measured over 6 hours using a static probe (CorreflowElectrostatic Monitor 3410™ available from Progression). The staticprobe was located within the polymerization reactor. The reactortemperature was also measured. Several similar runs were carried out atdifferent times to establish baseline run conditions prior to running aninventive example (see “baseline” Run Nos. 1, 3, 5, 6, 13 and 16 ofTable 1). Static of the solid catalyst entering the reactor was alsomeasured within the catalyst metering area over the 6 hour period.Relevant data for these examples are provided in Table 1.

EXAMPLES 2, 4, 7-12 AND 17 INVENTIVE RUNS

In each polymerization run, a Type 2 polymerization catalyst (each ofthe Type 2 Catalysts 2a-2e, are prepared as described above usingvarious amounts of a catalyst modifier) was placed under a N2 blanketand using a dry catalyst feeder, a small shot of supported catalyst wascontinuously added to a technical scale reactor via a feeding tube.Equilibrium polymerization conditions were established after a period of4 residence times. Once equilibrium conditions were established, thestatic level in the reactor was measured over 6 hours using a staticprobe (Correflow Electrostatic Monitor 3410 available from Progression).The static probe was located within the polymerization reactor. Duringthis time reactor temperature was also measured. Polymerization runsusing Type 2 catalysts are inventive runs (see “inventive”polymerization Run Nos. 2, 4, 7-12 and 17 in Table 1) and were carriedout soon after establishing appropriate baseline conditions. Static ofthe solid catalyst entering the reactor was also measured within thecatalyst metering area over the 6 hour period. An examination of thepolymer product obtained during each of these runs revealed a freeflowing powder without significant chunks or strings. Relevant data forthese examples are provided in Table 1.

EXAMPLES 14 AND 15 COMPARATIVE RUNS

To provide a comparison between adding catalyst modifier directly to thereactor and including a catalyst modifier in the catalyst formulation,polymerization runs were conducted in which the catalyst modifier wasadded to the reactor directly, instead of including the catalystmodifier in the polymerization catalyst (see “comparative” Run Nos. 14and 15). These examples were conducted in a manner analogous to Example1, except that once equilibrium polymerization conditions wereestablished, a catalyst modifier was fed to the reactor. The catalystmodifier was Atmer-163 which was diluted in hexanes to give a 1% byweight mixture and added via a manifold, into the reactor. In Example14, 25 ppm of Atmer-163 (per mass of polymer produced) was fed to thereactor. Once steady state was achieved, the reaction was held constantfor another 3-4 residence times, and then the static level in thereactor was measured over 6 hours. Reactor temperature was measured andthe static of the catalyst entering the reactor was measured within thecatalyst metering area over the 6 hour period. In Example 15, the levelof Atmer-163 fed to the reactor was increased from 25 ppm to 100 ppm(based on the weight of the polymer produced) and then the static levelwas measured over 6 hours. Reactor temperature and the static of thecatalyst entering the reactor were measured within the catalyst meteringarea over the 6 hour period. An examination of the polymer productobtained during Atmer-163 addition revealed a free flowing powderwithout significant chunks or strings. Relevant data for these examplesare provided in Table 1.

TABLE 1 Static Level, Catalyst Productivity and Reactor TemperatureRange Examples Catalyst Catalyst Productivity Catalyst Reactor Temp.(Poly. Catalyst Modifier in Modifier fed (g poly/ Static Static StandardRun No.)¹ Type Catalyst to Reactor g cat) Level² Level³ Deviation⁴  1(baseline) Type 1a none none 3209 0.045 0.71 1.2  2 (inventive) Type 2a1.5 wt % none 4423 0.020 0.39 0.4 Atmer-163  3 (baseline) Type 1a nonenone 4900 0.031 0.63 0.7  4 (inventive) Type 2b 1.5 wt % none 5346 0.0160.86⁵ 0.5 Armostat-1800  5 (baseline) Type 1a none none 3909 0.041 0.430.8  6 (baseline) Type 1a none none 4043 0.029 0.42 0.7  7 (inventive)Type 2b 1.5 wt % none 4238 0.022 0.26 0.4 Armostat-1800  8 (inventive)Type 2c 2.5 wt % none 6842 0.023 0.87⁶ 0.3 Armostat-1800  9 (inventive)Type 2c 2.5 wt % none 5418 0.023 0.32 0.3 Armostat-1800 10 (inventive)Type 2b 1.5 wt % none 5328 0.013 0.26 0.5 Armostat-1800 11 (inventive)Type 2d 3.5 wt % none 4751 0.019 0.34 0.3 Armostat-1800 12 (inventive)Type 2d 3.5 wt % none 5000 0.016 0.58⁷ 0.6 Armostat-1800 13 (baseline)Type 1a none none 3955 0.019 0.47 — 14 (comparative) Type 1a none 25 ppm3653 0.026 0.31 — Atmer-163 15 (comparative) Type 1a none 100 ppm 2760.027 0.29 — Atmer-163 16 (baseline) Type 1b none none 2300 0.023 0.230.41 17 (inventive) Type 2e 2.5 wt % none 3000 0.046 0.14 0.22Armostat-1800 Note ¹Pol. Run Nos 1-15 use a polymerization catalystbased on the phosphinimine complex(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂; Pol. Run Nos 16 and 17 use apolymerization catalyst based on the phosphinimine complex(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂. Note ²The static level of thecatalyst entering the reactor was measured by using a Correstat 3410static probe over a 6 hour period (or a 12 hour period for Pol Run Nos16 and 17). To obtain this value, a static signal, in nanoamps, isrecorded each second in the catalyst metering tube. These signals aretransformed into positive values by taking the absolute value of eachnumber. The sum of the absolute values is divided by the number ofseconds used to calculate the sum; this number is reported in Table 1.Note ³The static level of solids in the reactor was measured with aCorrestat 3410 static probe over a 6 hour period (or a 12 hour periodfor Pol Run Nos 16 and 17). To obtain this value, a static signal, innanoamps, is recorded each second at the reactor wall. These signals aretransformed into positive values by taking the absolute value of eachnumber. The sum of the absolute values is divided by the number ofseconds used to calculate the sum; this number is reported in Table 1.Note ⁴The standard deviation in temperature. Standard deviation of thereactor temperature is a way to quantify how much the reactortemperature fluctuates from the mean temperature or control temperature.A smaller standard deviation means smaller temperature fluctuationsaround the control temperature. A larger standard deviation means largertemperature fluctuations around the control temperature. In the data setgenerated for the patent, the standard deviation was calculated over 10hours of steady state operation (or a 12 hour period from Pol. Run Nos16 and 17). Note ⁵This run had a higher than expected reactor staticreading for unknown reasons. We note however, that the catalyst staticlevel and the size of the temperature excursion are both low relative tothe baseline case (Run. No. 3). Note ⁶An unexpected increase in staticsuddenly occurred during this run. Examination of the polymer showed asmall amount of roped material which may have artificially increased theoverall static measurement within the last 6 hours of this run. Anexamination of the static levels prior to the static spike wasconsistent with an overall static measurement of 0.49 (i.e. over theprevious 6 hours). Note ⁷An ethylene pressure supply problem createdpressure swings in the reactor which may have impacted the reactorstatic measurement.

The data in Table 1 shows that the inclusion of a catalyst modifier inthe phosphinimine based polymerization catalyst can improve catalystproductivity, and that to improve productivity, the preferred amounts ofcatalyst modifier added are somewhere from about 0.5 wt % to about 4.0wt % based on the weight of the polymerization catalyst. FIG. 1 alsoshows how optimizing the amount of catalyst modifier can increase thecatalyst productivity. The improvement in catalyst productivity wasobserved regardless of whether the phosphinimine catalyst used to makethe polymerization catalyst included a substituted cyclopentadienylligand (e.g. (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂) or a substitutedindenyl ligand (e.g. (1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂).

The data provided in Table 1 shows that inclusion of a catalyst modifierwithin the polymerization catalyst reduced at least one of: reactorstatic level, catalyst static level, and reactor temperature excursionsrelative to the polymerization catalyst not treated with a catalystmodifier. With the exception of Run No. 8 (in which a small amount ofpolymer rope was formed; see Note 6) visual examination of all polymerproducts obtained using a Type 2 catalyst revealed products which werefree flowing powders without significant chunks or strings. Hence, thedata show that reactor continuity and operability improve when acatalyst modifier is included in the polymerization catalystformulation.

Inclusion of the catalyst modifier in the polymerization catalystgenerally decreases the level of static measured in the reactor.Although there were a few exceptions to this trend (see polymerizationRun Nos. 4, 8, 12 and corresponding Notes 5, 6 and 7 respectively), wenote that in virtually all cases the catalyst static measured decreasedwhen a Type 2 catalyst was used relative to a Type 1 catalyst (theexception was polymerization Run No. 17). In all inventive Examplesusing a Type 2 catalyst (treated with a catalyst modifier), the reactortemperature excursions were smaller than when a Type 1 catalyst (nottreated with a catalyst modifier) was used.

For plots of reactor static observed over time for polymerization runsusing catalysts with and without catalyst modifier treatment see FIGS.2, 3, 4, 5, 6, 7, 10 and 11 which correspond to Polymerization Run Nos.1, 2, 6, 7, 9, 11, 16 and 17 respectively. For plots of reactor staticobserved over time for polymerization runs using the Type 1a catalyst(without catalyst modifier treatment), but where the catalyst modifierwas not added or added directly to the reactor see FIGS. 8 and 9 whichcorrespond to Polymerization Run Nos. 13 and 14 respectively.

The data in Table 1 also includes a comparison between adding thecatalyst modifier to the catalyst and adding the catalyst modifierdirectly to the reactor. It is clear that although addition of thecatalyst modifier directly to the reactor improves static levels andreactor operability relative to baseline conditions, it also negativelyimpacts the catalyst productivity to some degree, especially at higherloadings. Hence, the data in Table 1 indicate that only inclusion of thecatalyst modifier within the polymerization catalyst formulationprovides the dual improvement: higher catalyst productivity and betterreactor operability.

In addition to improvements in reactor operability, we have found thatinclusion of a catalyst modifier in the polymerization catalyst (oraddition of catalyst modifier directly to the reactor) may dramaticallyaffect copolymer product architecture while not significantly changingthe polymer density or melt index. The polymer properties of copolymersisolated from polymerization Run Nos. 2, 4, 6, 9, 11, 14, 16 and 17, areprovided below in Table 2.

TABLE 2 Polymer Properties Poly. Run No. 6 14 2 4 9 11 16 17 CatalystType 1a Type 1a Type 2a Type 2b Type 2c Type 2d Type 1b Type 2e Catalystnone none 1.5 wt % 1.5 wt % 2.5 wt % 3.5 wt % none 2.5 wt % Modifier inAtmer-163 Armostat-1800 Armostat-1800 Armostat-1800 Armostat-1800Catalyst Catalyst none 25 ppm none none none none none none Modifier fedAtmer-163 to Reactor Density 0.9182 0.9174 0.9189 0.9180 0.9186 0.91850.923 0.92 (g/cc) I₂(g/10 min) 1.01 1.03 0.89 1.03 0.90 0.93 0.6 0.54I₁₀/I₂ 5.78 5.63 5.76 5.64 5.64 5.66 9.55 10.6 I₂₁/I₂ 16.3 15.9 16.715.8 14.1 16.1 34.1 43.5 CDBI (wt %) 50.2 58.2 55.2 57.9 61.4 58.1 4647.2 TREF 20.4 15.3 20.9 16.7 15.4 17.0 25 20 (90-105° C., wt %) Mn52879 55077 50825 47455 53940 57167 23637 25053 Mw 103750 104231 109275100157 106495 106771 114502 120821 Mz 177076 179401 205446 164387 177080174086 330614 372081 Mw/Mn 1.96 1.89 2.15 2.11 1.97 1.87 4.84 4.82SCB/1000 10.4 10.9 9.6 10.1 10.0 10.3 10.9 13.3 C's mole % of C6 2.1 2.21.9 2.0 2.0 2.1 2.2 2.7 wt % of C6 6.00 6.20 5.5 5.80 5.70 5.90 6.3 7.6Comonomer 1-hexene 1-hexene 1-hexane 1-hexane 1-hexene 1-hexene 1-hexene1-hexene Comonomer normal flat reversed reversed reversed partiallyslightly highly Profile reversed reversed reversed (GPC-FTIR) Peak 118.5117.0 119.0 117.6 117.3 117.3 107.5/121.4 121.1 Melting Temperature (°C.) % 44.2 44.5 45.3 47.4 44.5 44.6 47.4 44.4 Crystallinity Hexane 0.210.19 0.22 0.22 0.27 0.26 0.52 0.72 Extractables (wt %)

The data in Table 2 shows that the “composition distribution” may bedifferent for copolymers made with a Type 2 catalyst relative tocopolymers made with a Type 1 catalyst. Indices which characterizechanges in “composition distribution” of the ethylene copolymer includechanges to one or more of the following: A) the composition distributionbreadth index (CDBI) of the ethylene copolymer as measured usingtemperature rising elution fractionation (TREF) methods; B) the weightpercent of a higher temperature eluting material (i.e. from 90° C. to105° C.) observed in TREF profile obtained for the ethylene copolymer;and C) the comonomer distribution profile (i.e. the comonomerincorporation vs. molecular weight) of the ethylene copolymer asmeasured by gel permeation chromatography with Fourier transformdetection (GPC-FTIR).

Examination of the data in Table 2 (compare for example Run No. 6 withRun Nos. 4, 9 and 11) shows that the amount of copolymer (in weightpercent) which elutes at 90-105° C. in a TREF analysis is lower when aType 2 catalyst (treated with Armostat-1800) is used than when a Type 1catalyst (no catalyst modifier) is used to copolymerize ethylene with1-hexene (an exception occurred during Run No. 2 using a Type 2 catalysttreated with Atmer-163 where the amount of copolymer (in weight percent)which eluted at 90-105° C. in a TREF analysis remained largelyunchanged). These results indicate that inclusion of the catalystmodifier in the polymerization catalyst improves short chain branching(i.e. comonomer) homogeneity. This fact is further evidenced by theincrease in CDBI observed with all the Type 2 catalysts tested.Comparison of Run No. 6 with Run Nos. 2, 4, 9 and 11 in Table 2 showsthat, for every case, the CDBI is higher when a Type 2 catalyst is usedrelative to a Type 1 catalyst. In fact, the CDBI is increased by atleast 5% in each case and more than 10% for the copolymer obtained inRun No. 9. The comonomer distribution profile is also changed when acatalyst modifier is present in the polymerization catalyst. When a Type2 catalyst is employed, the amount of comonomer incorporation at highermolecular weights relative to lower molecular weights (as measured byGPC-FTIR) is higher than the amount of comonomer incorporation at highermolecular weights relative to lower molecular weights when a Type 1catalyst is used (Table 2 shows that the comonomer distribution changesfrom a normal profile to a flat, reversed or partially reversed profile,or from a slightly reversed profile to a highly reversed profile, when acatalyst modifier is present in the polymerization catalyst). Increasingthe amount of comonomer incorporation at higher molecular weights mayimprove polymer end use properties such as dart impact, punctureresistance, optical properties, and hot tack or seal performance.

Finally we note that inclusion of a catalyst modifier in thepolymerization catalyst improved the gel properties of cast film madefrom ethylene copolymers obtained with such catalysts (i.e. Type 2Catalysts). The gel properties of copolymers isolated from selectedpolymerization runs are provided below in Table 3.

TABLE 3 Gels in Cast Film Poly. Catalyst Modifier Catalyst Modifier OCSGel Count Run No. in Catalyst fed to Reactor (ppm) 5 none None 83 6 noneNone 141 7 1.5 wt % None 9 Armostat-1800 9 2.5 wt % None 6 Armostat-180011 3.5 wt % None 7 Armostat-1800 14 none 25 ppm 13 Atmer-163

Table 3 shows that use of a Type 1 Catalyst (no catalyst modifier) givescopolymer product which when cast into film has high gels counts (83 and141 for baseline runs 5 and 6) while use of a Type 2 Catalyst (includesa catalyst modifier) gives copolymer product which has a gel count ofbelow 10 when cast into film.

The Effect of the Order of Addition of Catalyst Components

In the next set of examples, the order of addition of catalystcomponents to an inert support was changed to examine whether there wasany effect in terms of catalyst flowability, catalyst polymerizationperformance, and the resulting polymer architecture. Polymerizationcatalysts which were modified with Armostat-1800™ and based on eitherthe (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ phosphinimine catalystcompound or the (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ phosphiniminecatalyst compound were examined. Polymerization catalysts based on1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ are coded A1-A5. Polymerizationcatalysts based on (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ are coded B1-B3.

Catalyst A1 (Standard Order of Addition of a Catalyst Modifier). In aglovebox, into a 3 L, three-neck round bottom flask equipped with anoverhead stirrer was added 490 mL toluene. While the solvent wasstirred, 122.5 g of dehydrated silica was added. Next, 233.8 g of amethylaluminoxane (MAO) in toluene solution containing 4.5 wt % Al wasadded into the flask by cannula over a period of 10 minutes whilestirring was maintained. The MAO solution container was rinsed threetimes with 25 mL of toluene and the rinsings were added into the flask.The slurry was stirred for 2 hours at room temperature. A solution of2.28 g of (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ in 46 mL toluene wasthen added into the flask over a period of 5 minutes. The slurry wasstirred for 2 hours at ambient temperature. Next, 24.84 g of a 16.4 wt %Armostat-1800/toluene solution was added into the flask over a period of5 minutes. The catalyst modifying agent solution container was rinsedwith toluene (3×5 mL), and the rinsings were added in the flask. Theslurry was further stirred at ambient temperature for 30 minutes. Thecatalyst slurry was poured into a fritted funnel, which was fitted ontoa filter flask, and vacuum applied to the filter flask to separate thereaction solvent. Next, 225 mL of pentane was added to the filter cakeand stirred with spatula to obtain a well dispersed slurry. Reducedpressure was then applied to the filter flask to remove the washsolvent. A second pentane wash was done and vacuum applied to removesolvent until the filter cake appeared to be dry. The filter cake wasthen transferred to a 2 L round-bottomed flask and the catalyst wasdried by applying reduced pressure to the flask until <250 mTorr wasobtained.

Catalyst A2 (Reverse Order of Addition of a Catalyst Modifier).

In a glovebox, into a 3 L, three-neck round bottom flask equipped withan overhead stirrer was added 327 mL toluene. While the solvent wasstirred, 81.7 g dehydrated silica was added. Next, 16.6 g of a 16.4 wt %Armostat-1800/toluene solution was added into the flask over a period of5 minutes. The catalyst modifying agent solution container was rinsedwith toluene (3×5 mL), and the rinsings were added in the flask. Theslurry was further stirred at ambient temperature for 30 minutes. Next,155.9 g of a MAO in toluene solution containing 4.5 wt % Al was addedinto the flask by cannula over a period of 10 minutes while stirring wasmaintained. The MAO solution container was rinsed three times, each with25 mL toluene and the rinsings were added into the flask. The slurry wasstirred for 2 hours at room temperature. A solution of 1.52 g of(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ dissolved in 30 mL toluene wasthen added into the flask over a period of 5 minutes. The slurry wasstirred for 2 hours at ambient temperature. The catalyst slurry waspoured into a fritted funnel, which was fitted onto a filter flask, andvacuum was applied to the filter flask to separate the reaction solvent.150 mL pentane was added to the filter cake and stirred with spatula toobtain a well dispersed slurry. Reduced pressure was then applied to thefilter flask to remove wash solvent. A second pentane wash was done andvacuum was applied to remove solvent until the filter cake appears to bedry. The filter cake was then transferred to a 2 L round-bottomed flaskand the catalyst was dried by applying reduced pressure to the flaskuntil 350 mTorr was obtained.

Catalyst A3 (Reverse Order of Addition of a Catalyst Modifier-Repeat).In a 3 L, three-neck round bottom flask equipped with an overheadstirrer was added toluene (330 mL). While the stirrer was maintained at200 rpm, dehydrated silica (76.069 g) was added. A 15 wt % Armostat-1800in toluene solution (18.106 g) was added into the flask over a period of3 minutes. The container was rinsed with toluene (2×5 mL), and therinsings were added to the flask. The slurry was further stirred atambient temperature for 30 minutes. A 10 wt % MAO in toluene solution(195.625 g) was added into the flask by cannula over a period of 13minutes while stirring was maintained. The MAO solution container wasrinsed with toluene (2×25 mL), and the rinsings were added to the flask.The slurry was stirred for 2 hours at room temperature. Thephosphinimine catalyst compound(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (1.765 g) was then added intothe flask in solid form over a period of 4 minutes. The slurry wasstirred for 2 hours at ambient temperature. The catalyst slurry waspoured into a fritted funnel, which was fitted onto a filter flask, andreduced pressure applied to the filter flask to separate the reactionsolvent. Toluene (150 mL) was added to the filter cake and stirred witha spatula to obtain a well-dispersed slurry. Reduced pressure was thenapplied to the filter flask to remove the wash solvent. Pentane (150 mL)was added to the filter cake and stirred with spatula to obtain a welldispersed slurry. Reduced pressure was then applied to the filter flaskto remove wash solvent. A second pentane wash was done and reducedpressure applied to remove solvent until the filter cake appeared to bedry. The filter cake was then transferred to a 2 L round-bottomed flaskand the catalyst was dried by applying reduced pressure to the flaskuntil 350 mTorr was obtained.

Catalyst A4 (Semi-Reversed Order of Addition of a Catalyst Modifier). Toa 3 L, three-neck round bottom flask equipped with an overhead stirrerwas added toluene (330 mL). While the stirrer was maintained at 200 rpm,dehydrated silica (76.08 g) was added. A 10 wt % MAO in toluene solution(195.62 g) was added into the flask by cannula over a period of 13minutes while stirring was maintained. The MAO solution container wasrinsed with toluene (2×25 mL), and the rinsings were added into theflask. The slurry was stirred for 2 hours at room temperature. A 15 wt %Armostat-1800 in toluene solution (18.1 g) was added into the flask overa period of 3 minutes. The container was rinsed with toluene (2×5 mL),and the rinsings were added in the flask. The slurry was further stirredat ambient temperature for 30 minutes. The phosphinimine catalystcompound (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (1.76 g) was thenadded into the flask in solid form over a period of 5 minutes. Theslurry was stirred for 2 hours at ambient temperature. The catalystslurry was poured into a fritted funnel, which was fitted onto a filterflask, and reduced pressure applied to the filter flask to separate thereaction solvent. Toluene (150 mL) was added to the filter cake andstirred with a spatula to obtain a well dispersed slurry. Reducedpressure was then applied to the filter flask to remove the washsolvent. Pentane (150 mL) was added to the filter cake and stirred withspatula to obtain a well dispersed slurry. Reduced pressure was thenapplied to the filter flask to remove wash solvent. A second pentanewash was done and reduced pressure applied to remove solvent until thefilter cake appeared to be dry. The filter cake was then transferred toa 2 L round-bottomed flask and the catalyst was dried by applyingreduced pressure to the flask until 450 mTorr was obtained.

Catalyst A5 (Split Addition of a Catalyst Modifier: 50 Wt % before MAOand 50 Wt % after the Phosphinimine Catalyst Compound). To a 3 L,three-neck round bottom flask equipped with an overhead stirrer wasadded toluene (330 mL). While the stirrer was maintained at 200 rpm,dehydrated silica (76.018 g) was added. A 15 wt % Armostat-1800 intoluene solution (9.056 g) was added into the flask over a period of 2minutes. The container was rinsed with toluene (2×3 mL), and therinsings were added to the flask. The slurry was further stirred atambient temperature for 30 minutes. A 10 wt % MAO in toluene solution(204.126 g) was added into the flask by cannula over a period of 15minutes while stirring was maintained. The MAO solution container wasrinsed with toluene (2×25 mL), and the rinsings were added into theflask. The slurry was stirred for 2 hours at room temperature. Thephosphinimine catalyst compound(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (1.765 g) was then added tothe flask in solid form over a period of 4 minutes. The slurry wasstirred for 2 hours at ambient temperature. A 15 wt % Armostat-1800 intoluene solution (9.05 g) was added into the flask over a period of 1minute. The container was rinsed with toluene (2×3 mL), and the rinsingswere added to the flask. The slurry was further stirred at ambienttemperature for 30 minutes. The catalyst slurry was poured into afritted funnel, which was fitted onto a filter flask, and reducedpressure applied to the filter flask to separate the reaction solvent.Toluene (150 mL) was added to the filter cake and stirred with a spatulato obtain a well dispersed slurry. Reduced pressure was then applied tothe filter flask to remove the wash solvent. Pentane (150 mL) was addedto the filter cake and stirred with spatula to obtain a well dispersedslurry. Reduced pressure was then applied to the filter flask to removewash solvent. A second pentane wash was done and reduced pressureapplied to remove solvent until the filter cake appeared to be dry. Thefilter cake was then transferred to a 2 L round-bottomed flask and thecatalyst was dried by applying reduced pressure to the flask until 350mTorr was obtained.

Catalyst B1 (Standard Order of Addition of a Catalyst Modifier). In aglovebox, into a 5 L, three-neck round bottom flask equipped with anoverhead stirrer was added 1.7 L toluene. While the solvent was stirred,381.9 g dehydrated silica was added. Next, 1049.3 g of a MAO in toluenesolution containing 4.5 wt % Al was added into the flask by cannula overa period of 55 minutes while stirring was maintained. The MAO solutioncontainer was rinsed three times, each with 25 mL toluene and therinsings were added to the flask. The slurry was stirred for 2 hours atroom temperature. A solution of 7.88 g(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ in 600 mL toluene was then addedinto the flask over a period of 25 minutes. The slurry was stirred for 2hours at ambient temperature. Next, 67.77 g of a 18.55 wt %Armostat-1800/toluene solution was added to the flask over a period of15 minutes. The catalyst modifying agent solution container was rinsedwith toluene (3×25 mL), and the rinsings were added to the flask. Theslurry was further stirred at ambient temperature for 30 minutes. Thecatalyst slurry was poured into a fritted funnel, which was fitted ontoa filter flask, and vacuum was applied to the filter flask to separatethe reaction solvent. Next, 2000 mL of pentane was added to the filtercake and stirred with spatula to obtain a well dispersed slurry. Reducedpressure was then applied to the filter flask to remove wash solvent.The filter cake was then transferred to a 3 L round-bottomed flask andthe catalyst was dried by applying reduced pressure to the flask until450 mTorr was obtained.

Catalyst B2 (Reverse Order of Addition of a Catalyst Modifier). In aglovebox, into a 3 L, three-neck round bottom flask equipped with anoverhead stirrer was added 327 mL toluene. While the solvent wasstirred, 81.8 g dehydrated silica was added. Next, 16.8 g of a 15.0 wt %Armostat-1800/toluene solution was added to the flask over a period of 1minute. The catalyst modifying agent solution container was rinsed withtoluene (3×5 mL), and the rinsings were added to the flask. The slurrywas further stirred at ambient temperature for 30 minutes. Next, 155.9 gof a MAO in toluene solution containing 4.5 wt % Al was added to theflask by cannula over a period of 10 minutes while stirring wasmaintained. The MAO solution container was rinsed three times withtoluene and the rinsings were added into the flask. The slurry wasstirred for 2 hours at room temperature. A solution of 1.58 g(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ dissolved in 32 mL of toluene wasthen added into the flask over a period of 3 minutes. The slurry wasstirred for 2 hours at ambient temperature. The catalyst slurry waspoured into a fritted funnel, which was fitted onto a filter flask, andvacuum applied to the filter flask to separate the reaction solvent.Next, 150 mL of pentane was added to the filter cake and stirred withspatula to obtain a well dispersed slurry. Reduced pressure was thenapplied to the filter flask to remove wash solvent. A second pentanewash was done and vacuum applied to remove solvent until the filter cakeappeared to be dry. The filter cake was then transferred to a 2 Lround-bottomed flask and the catalyst was dried by applying reducedpressure to the flask until 350 mTorr was obtained.

Catalyst B3 (Reverse Order of Addition of a Catalyst Modifier-Repeat).In a glovebox, into a 3 L, three-neck round bottom flask equipped withan overhead stirrer was added 309 mL toluene. While the solvent wasstirred, 77.3 g dehydrated silica was added. 13.6 g of a 18.55 wt %Armostat-1800/toluene solution was added into the flask over a period of5 minutes. The catalyst modifying agent solution container was rinsedwith toluene (3×5 mL), and the rinses were added to the flask. Theslurry was further stirred at ambient temperature for 30 minutes. 200.9g of a MAO in toluene solution containing 4.5 wt % Al was added into theflask by cannula over a period of 6 minutes while stirring wasmaintained. The MAO solution container was rinsed three times, each with25 mL toluene and the rinses were added into the flask. The slurry wasstirred for 2 hours at room temperature. A solution of 1.58 g(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ complex dissolved in 32 mL toluenewas then added into the flask over a period of 4 minutes. The slurry wasstirred for 2 hours at ambient temperature. The catalyst slurry waspoured into a fritted funnel, which was fitted onto a filter flask, andvacuum applied to the filter flask to separate the reaction solvent. 150mL toluene was added to the filter cake and stirred with spatula toobtain a well dispersed slurry. Reduced pressure was then applied to thefilter flask to remove wash solvent. 150 mL pentane was added to thefilter cake and stirred with spatula to obtain a well dispersed slurry.Reduced pressure was then applied to the filter flask to remove washsolvent. A second pentane wash was done and vacuum applied to removesolvent until the filter cake appears to be dry. The filter cake wasthen transferred to a 2 L round-bottomed flask and the catalyst wasdried by applying reduced pressure to the flask until 450 mTorr wasobtained.

Polymerization Catalyst Flowability

The polymerization catalyst flow properties were assessed using a“Flodex™” test instrument purchased from Hanson Research Corporation.The Flodex test instrument utilizes a cylinder with a series ofreplaceable discs placed at the bottom with a hole of differingdiameters at the center of each of the different discs. The disc hole iscovered with a shutter. After 40 g of the polymerization catalyst ispoured into the cylinder, the shutter covering the hole is releasedallowing the sample to fall through the hole. The diameter inmillimeters of the smallest hole through which the polymerizationcatalyst sample falls through three times out of three attempts is takenas the “Flodex”. The smaller the Flodex value, the better the solidpolymerization catalyst flows though the Flodex instrument. The lowerthe Flodex number, the better the solid polymerization catalyst isexpected to flow from the catalyst feeder and associated catalyst feedlines to the polymerization reactor.

Table 4 compares the catalyst flowability as measured using a Flodex™instrument for polymerization catalysts made by adding Armostat-1800 toa silica support after the phosphinimine catalyst and the cocatalystcomponents have been added (see Catalysts A1 and B1) with polymerizationcatalysts made by adding the Armostat-1800 to a silica support beforethe phosphinimine catalyst and the cocatalyst components have been added(see Catalysts A2, A3, B2 and B3).

TABLE 4 Weight % Armostat- 1800 (based on weight of the inert Cata-support, phosphinimine Flodex lyst Catalyst Formula catalyst andcocatalyst) (mm) A1 (1,2-(n- 2.7 20-22 propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ A2 (1,2-(n- 2.7 9 propyl)(C₆F₅)Cp)Ti(N═P(t- Bu)₃)Cl₂ A3(1,2-(n- 2.7 8 propyl)(C₆F₅)Cp)Ti(N═P(t- Bu)₃)Cl₂ A4 (1,2-(n- 2.7 18propyl)(C₆F₅)Cp)Ti(N═P(t- Bu)₃)Cl₂ A5 (1,2-(n- 2.7 20propyl)(C₆F₅)Cp)Ti(N═P(t- Bu)₃)Cl₂ B1 (1-C₆F₅CH₂-Indenyl)((t- 2.5 16Bu)₃P═N)TiCl₂ B2 (1-C₆F₅CH₂-Indenyl)((t- 2.5 8 Bu)₃P═N)TiCl₂ B3(1-C₆F₅CH₂-Indenyl)((t- 2.5 4 Bu)₃P═N)TiCl₂

Continuous ethylene/1-hexene gas phase copolymerization experimentsusing catalysts A1-A5 and B1-B3, were conducted in a 56.4 litertechnical scale reactor (TSR) in continuous gas phase operation (for anexample of a TSR reactor set up see Eur. Pat. Appl. No. 659,773A1).Ethylene polymerizations were run at 80-85° C. and a total operatingpressure of 300 pounds per square inch gauge (psig). Gas phasecompositions for ethylene, 1-hexene and hydrogen were controlled viaclosed-loop process control to values of 35-65, 0.5-2.1 and 0.018-0.055mole percent, respectively. Nitrogen constituted the remainder of thegas phase mixture. Typical production rate for these conditions was 2.0to 3.0 kg of polyethylene per hour. Triethylaluminum (TEAL) may be fedto the reactor continuously, as a 0.25 wt % solution in hexane (solutionfed at about 10 mL/hr) in order to scavenge impurities or experimentscan be carried out without a scavenger. The residence time in thereactor is held at 1.5-3.0 hr, with a production rate range from 1.5-2.8kg/hr. Selected polymerization conditions and polymer data are providedin Tables 5 and 6 respectively (note: C2=ethylene; C6=1-hexene;H2=hydrogen).

TABLE 5 Production Residence Ethylene C6/C2 H2/C2 Bulk Rate Time, Temp.in Reactor, Molar C6/C2 Molar Density Catalyst (kg/hour) (hours) (° C.)(mol %) Flow by GC Flow (lb/ft³) A1 2.50 1.60 85 50 0.0215 — 0.0003 — A22.57 1.55 85 50 0.0212 0.0215 0.0003 — A3 2.50 1.60 85 50 0.0213 0.0190.0003 24.1 A4 2.49 1.63 85 50 0.0213 0.0226 0.0003 20.4 A5 1.98 2.03 8550 0.0213 0.0233 0.0003 22.1 B1 2.39 1.91 80 65 0.0236 0.0206 0.0012 —B2 2.20 2.02 80 50 0.0215 0.0141 0.0011 23.9 B3 2.50 1.80 80 65 0.02000.0141 0.0012 —

TABLE 6 Melt Density MI CDBI-50 Wt % HD Strength Catalyst (g/cm³) (g/10min) Mw/Mn I₂₁/I₂ (wt %) (90-105° C.) (cN) A1 0.9177 0.91 — — — — — A20.9172 1.11 1.89 15.4 64.2 12.9 2.43 A3 0.917 1.33 1.87 15.6 62.9 10.41.94 A4 0.9176 0.97 2.0  15.1 67.6 11.8 2.51 A5 0.9162 1.12 1.75 15.468.2 11.1 2.18 B1 0.9206 0.86 4.62 36.7 46.4 19.2 5.04 B2 0.9196 0.574.56 40.2 52   18   — B3 0.92 0.63 — — — — —

The data in Table 4 shows that when using a reversed order of additionof the catalyst modifier (i.e. adding the catalyst modifier to thesupport before the phosphinimine catalyst and cocatalyst components),whether the polymerization catalyst be based on either the(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ or the(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ phosphinimine catalysts, theflowability of the polymerization catalyst improves considerably asevidenced by the decrease in the Flodex number. Compare for example, theFlodex value for Catalyst A1 with Catalyst A2 or A3. The Flodex dropsfrom about 20 mm to about 9 mm and 8 mm respectively. Also compare theFlodex of Catalyst B1 with Catalyst B2 or B3, where the Flodex valuedrops from about 16 mm to 8 mm and 4 mm respectively. In addition, thedata show, that if the catalyst modifier is added to an inert support(e.g. silica) after the cocatalyst (e.g. MAO), but before the activecatalyst compound (a phosphinimine catalyst), then the Flodex remainslargely unchanged. Compare Catalyst A1 with Catalyst A4, where theFlodex only drops from about 20 mm to about 18 mm. Finally, if thecatalyst modifier is added both before and after the cocatalyst andphosphinimine catalyst components are added to the inert support, theFlodex remains unaffected. Compare Catalyst A1 in which all of thecatalyst modifier is added after both the cocatalyst and thephosphinimine catalyst complex, with Catalyst A5 in which the catalystmodifier was split into equal portion additions to the inert support,with half being added before the cocatalyst and phosphinimine complex,and half being added to the inert support after the cocatalyst andphosphinimine catalyst. For A1 and A5 the Flodex value is the same.

The reactor operability of polymerization catalysts A1 and A2 isillustrated in FIGS. 12 and 13 respectively. They show plots of theproduction rate (dotted black line) in kg of polymer/hour vs. time aswell as the catalyst feeder output rate (solid black line) in percentageof the maximum rotation speed of the variable-speed motor of thecatalyst feeder (which corresponds to the rotation speed of the disk inthe catalyst feeder) vs. time. In the TSR scale polymerization, thedesired production rate of approximately 2.5 kg/hr is reached byadjusting the catalyst feeder output. If the catalyst flows well to thereactor and shows reasonable activity, the catalyst feeder output doesnot need to be heavily adjusted to meet target productivity levels. Inthis sense, the operability of catalyst A2 was found to be better thancatalyst A1, because for catalyst A2 the desired production rate wasreached relatively quickly with no major adjustments in the catalystfeeder output as shown in FIG. 13. The polymerization ran smoothly andwith well controlled reactor temperatures. In contrast, for catalyst A1,the polymerization production rate only took off after several hours andonly while major increments in catalyst feeder output were being made.This led to a temperature runaway (not shown in FIG. 12, but indicatedby the rapid increase in polymerization production rate toward the endof the run) and the polymerization run had to be aborted. The improvedperformance of catalyst A2 over catalyst A1 was consistent with theFlodex measurements shown in Table 4. The lower Flodex number associatedwith Catalyst A2, corresponded to a lower and more steady catalystfeeder output rate at the same polymer production rate as that observedwith Catalyst A1 (Compare FIG. 13 with FIG. 12), which in turn indicatedbetter filling efficiency of the catalyst feeder disk holes and bettercatalyst feeding generally. The catalyst feeder used is similar to thatdescribed in U.S. Pat. No. 3,779,712 and U.S. Pat. No. 3,876,602. Thecatalyst feeder delivers catalyst by aligning a rotating disk with holesto an opening in the catalyst reservoir from which catalyst drops intothe holes. The disk rotates further until it aligns with the inlet of anentrainment chamber into which the catalyst drops and is carried awaywith nitrogen to the reactor. A percentage of the feeder output relatesto the speed to which the feeder disk rotates. Higher feeder outputequals higher rotation speed and therefore more catalyst being deliveredas a function of time. The actual percentage of feeder output setcorresponds to a percentage of the maximum rotation speed of thevariable-speed motor, which in turn determines the rotation speed of theperforated catalyst feeder disk.

The reactor operability of polymerization catalysts B1, B2 and B3 isillustrated in FIGS. 14, 15 and 16 respectively. The Figures show plotsof the production rate (dotted black line) in kg of polymer/hour vs.time, as well as the catalyst feeder output rate (solid black line)given in percentage of the maximum rotation speed of the variable-speedmotor of the catalyst feeder (which corresponds to the rotation speed ofthe disk in the catalyst feeder) vs. time. As discussed above, in theTSR scale polymerization, the desired production rate of approximately2.5 kg/hr is reached by adjusting the catalyst feeder output. If thecatalyst flows well to the reactor and shows comparable activity, thecatalyst feeder output does not need to be heavily adjusted to meettarget productivity levels.

For Catalyst B1, the catalyst feeder output was increased to reach apolymer production rate of approximately 2.5 kg/hr, but it was difficultto maintain a constant production rate despite a constant catalystfeeder output (see FIG. 14). This was attributed to erratic catalystdelivery to the reactor.

For Catalysts B2, and B3, the desired polymer production rate ofapproximately 2.5 kg/hr was more quickly obtained and was more constantwhile catalyst feeder output was held relatively constant (see FIGS. 15and 16). This was attributed to smoother catalyst delivery to thereactor. Catalysts B2 and B3 also showed reduced reactor temperaturevariance and less reactor fouling than catalyst B1. Without wishing tobe bound by theory, we speculate that the better reactor performance wasdue to a more consistent catalyst delivery to the reactor. Thedifferences in the catalyst flowability between catalyst B1 andcatalysts B2 and B3 were consistent with the Flodex measurements shownin Table 4. The lower Flodex numbers shown in Table 4 for catalysts B2and B3, corresponded to lower catalyst feeder output rates in order toachieve the same polymer production rate and catalyst productivity asthat obtained with catalyst B1. This supports the notion that forcatalyst B2 and B3 there is better filling efficiency of the catalystfeeder disk holes in the catalyst feeder and better catalyst feedinggenerally.

The above results show that the polymerization catalyst feeding andreactor operability at the TSR scale improved when using a reverse orderof addition of the catalyst modifier (i.e. the catalyst modifier isadded to a silica support prior to the addition of a phosphiniminecatalyst and a cocatalyst). For the polymerization catalysts A2, theflowability of the catalyst to the reactor appeared to be better thanfor polymerization catalyst A1. For the polymerization catalysts B2 andB3, a similar improvement in catalyst flow to the reactor was observedrelative to catalyst B1.

Unexpectedly, both catalyst types A and B prepared with reverse order ofcatalyst modifier addition produced ethylene copolymers with differentcharacteristics than those made when the standard order of addition ofcatalyst modifier was used.

With reference to FIG. 17, it is clear that with polymerization catalystA1 which is prepared so that the catalyst modifier is added to the inertsupport last, the GPC-FTIR profile is consistent with a generallyreversed comonomer incorporation profile, in which short chain sidechain branching increases as the molecular weight of the polymerincreases. With reference to FIG. 18a and FIG. 18b , a person skilled inthe art will recognize that polymerization catalysts A2, and A3respectively, which are prepared by adding the catalyst modifier to thesupport prior to the phosphinimine catalyst and the cocatalystcomponents, the GPC-FTIR is consistent with a generally flat (or evenslightly negative) comonomer incorporation. That is, the short sidechain branching stays relatively constant (or decreases slightly) withincreasing molecular weight. Hence, a comparison between FIG. 17 andFIGS. 18a /18 b, shows that simply by changing the order of addition ofthe catalyst components, namely by adding the catalyst modifier to thesupport, before the addition of the phosphinimine catalyst and thecocatalyst components, a different polymer architecture can be obtained.

With reference to FIG. 19, a distinctly trimodal TREF profile isobserved when an ethylene copolymer is made with polymerization catalystB1 which is prepared by adding the catalyst modifier to the supportafter both the phosphinimine catalyst and the cocatalyst. In contrast,and with reference to FIG. 20, which shows the TREF profile of anethylene copolymer made using polymerization catalyst B3, which isprepared by adding the catalyst modifier to the support first, beforethe phosphinimine catalyst and cocatalyst components, two prevailingpeak areas are observed. Further, the temperatures at which the lowestelution peak temperature occurs in the TREF profile shifts by close to10° C. (higher) when using polymerization catalyst B3 instead ofpolymerization catalyst B1. Comparing the TREF profiles in FIGS. 19 and20, shows that changing the order in which the catalyst modifier isadded to formulate the polymerization catalyst has an effect on theresulting polymer architecture. The results show that different polymerscan be obtained, depending on how the polymerization catalyst issynthesized.

What is claimed is:
 1. A polymerization process comprising contactingethylene and at least one alpha olefin with a polymerization catalyst ina gas phase reactor, the polymerization catalyst comprising: i) aphosphinimine catalyst, ii) an inert support, iii) a cocatalyst, and iv)a catalyst modifier; wherein the catalyst modifier is present in from0.25 to 6.0 weight percent based on the weight of i), ii), and iii) ofthe polymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is0, each n is independently an integer from 1 to 30 when y is 2, and n isan integer from 1to 30 when y is 1; and wherein the polymerizationcatalyst is prepared by adding all of the catalyst modifier to the inertsupport prior to the addition of the phosphinimine catalyst and prior tothe addition of the cocatalyst; wherein the phosphinimine catalyst hasthe formula: (1,2-(R*)(Ar—F)Cp)Ti(N═P(t-Bu)₃)X₂, where R* is a straightchain alkyl group, Ar—F is a perfluorinated phenyl group, a 2,6 fluorosubstituted phenyl group, a 2,4,6 fluoro substituted phenyl group, or a2,3,5,6 fluoro substituted phenyl group, and X is an activatable ligand.2. The process of claim 1, wherein the catalyst modifier is present infrom 0.5 to 4.5 weight percent based on the weight of i), ii) and iii)of the polymerization catalyst.
 3. The process of claim 1 wherein thecatalyst modifier comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, and n and m are integers from 1 to 20.4. The process of claim 1 wherein the catalyst modifier comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and n isindependently an integer from 1-20.
 5. The process of claim 1 whereinthe catalyst modifier comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and n is 2 or
 3. 6. The process of claim 1 whereinthe catalyst modifier comprises at least one compound represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to22 carbon atoms.
 7. The process of claim 1 wherein the catalyst modifiercomprises a compound represented by the formula: C₁₈H₃₇N (CH₂CH₂OH) ₂.8. The process claim 1 wherein the catalyst modifier comprises compoundsrepresented by the formulas: C₁₃H₂₇N (CH₂CH₂OH) ₂ and C₁₅H₃₁N (CH₂CH₂OH)₂ .
 9. The process of claim 1 wherein the catalyst modifier is a mixtureof compounds represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹ is ahydrocarbyl group having from 8 to 18 carbon atoms.
 10. The process ofclaim 1 wherein the cocatalyst is selected from ionic activators,alkylaluminoxanes and mixtures thereof.
 11. The process of claim 1wherein the inert support is silica.
 12. A polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.25 to 6.0 weight percent based on the weight of i),ii) and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹is a hydrocarbylgroup having from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbylgroup having from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1,y is 2 when x is 0, each n is independently an integer from 1 to 30 wheny is 2, and n is an integer from 1 to 30 when y is 1; and wherein thepolymerization catalyst is prepared by adding all of the catalystmodifier to the inert support prior to the addition of the phosphiniminecatalyst and prior to the addition of the cocatalyst; wherein thephosphinimine catalyst has the formula: (1,2-(R*)(Ar—F)Cp)Ti(N═P(t-Bu)₃)X₂, where R* is a straight chain alkyl group,Ar—F is a perfluorinated phenyl group, a 2,6 fluoro substituted phenylgroup, a 2,4,6 fluoro substituted phenyl group, or a 2,3,5,6 fluorosubstituted phenyl group, and X is an activatable ligand.
 13. Thecatalyst of claim 12 wherein the catalyst modifier is present in from1.0 to 4.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst.
 14. The catalyst of claim 12 wherein thecatalyst modifier comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl grouphaving anywhere from 5 to 30 carbon atoms, and n and m are integers from1 to
 20. 15. The catalyst of claim 12 wherein the catalyst modifiercomprises at least one compound represented by the formula:R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6 to 30carbon atoms, and n is independently an integer from 1 to
 20. 16. Thecatalyst of claim 12 wherein the catalyst modifier comprises at leastone compound represented by the formula: R¹N((CH₂)_(n)OH)₂ where R¹ is ahydrocarbyl group having from 6 to 30 carbon atoms, and n is 2 or
 3. 17.The catalyst of claim 12 wherein the catalyst modifier comprises atleast one compound represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹is a hydrocarbyl group having from 8 to 22 carbon atoms.
 18. Thecatalyst of claim 12 wherein the catalyst modifier comprises a compoundrepresented by the formula: C₁₈H₃₇N(CH2CH2OH)₂.
 19. The catalyst claim12 wherein the catalyst modifier comprises compounds represented by theformulas: C₁₃H₂₇N (CH₂CH₂OH) ₂ and C₁₅H₃₁N (CH₂CH₂OH)₂.
 20. The catalystof claim 12 wherein the catalyst modifier is a mixture of compoundsrepresented by the formula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbylgroup having from 8 to 18 carbon atoms.
 21. The catalyst of claim 12wherein the cocatalyst is selected from ionic activators,alkylaluminoxanes and mixtures thereof.
 22. The catalyst of claim 12wherein the inert support is silica.